Structurally-colored articles and methods of making and using structurally-colored articles

ABSTRACT

Components of articles that include an optical element that imparts structural color to the component are provided. Methods of making the components including the optical element, and methods of using the components such as to make an article of manufacture are provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 17/176,057, having the title “STRUCTURALLY-COLORED ARTICLES ANDMETHODS OF MAKING AND USING STRUCTURALLY-COLORED ARTICLES,” filed onFeb. 15, 2021, which is a continuation application of U.S. applicationSer. No. 16/648,887, having the title “STRUCTURALLY-COLORED ARTICLES ANDMETHODS OF MAKING AND USING STRUCTURALLY-COLORED ARTICLES,” filed onMar. 19, 2020, now issued as U.S. Pat. No. 10,955,587, which is the 35U.S.C. § 371 National Stage application of International Application No.PCT/US2018/053529, filed Sep. 28, 2018, which claims the benefit of andpriority to U.S. Provisional Application Ser. No. 62/633,666, having thetitle “ARTICLES HAVING STRUCTURAL COLOR AND METHODS AND SYSTEMS FORMAKING ARTICLES HAVING STRUCTURAL COLOR,” filed on Feb. 22, 2018; U.S.Provisional Application Ser. No. 62/565,313, having the title“STRUCTURES HAVING STRUCTURAL COLOR AND METHODS AND SYSTEMS FOR MAKINGSTRUCTURES HAVING STRUCTURAL COLOR,” filed on Sep. 29, 2017; U.S.Provisional Application Ser. No. 62/565,310, having the title“STRUCTURES HAVING STRUCTURAL COLOR AND METHODS AND SYSTEMS FOR MAKINGSTRUCTURES HAVING STRUCTURAL COLOR,” filed on Sep. 29, 2017; U.S.Provisional Application Ser. No. 62/565,306, having the title“STRUCTURALLY COLORED STRUCTURES AND ARTICLES, METHODS OF MAKINGSTRUCTURES AND ARTICLES,” filed on Sep. 29, 2017; and U.S. ProvisionalApplication Ser. No. 62/565,299, having the title “STRUCTURALLY COLOREDARTICLES AND METHODS OF MAKING STRUCTURALLY COLORED ARTICLES,” filed onSep. 29, 2017, the disclosures which are incorporated herein byreference in their entireties.

BACKGROUND

Structural color is caused by the physical interaction of light with themicro- or nano-features of a surface and the bulk material as comparedto color derived from the presence of dyes or pigments that absorb orreflect specific wavelengths of light based on the chemical propertiesof the dyes or pigments. Color from dyes and pigments can be problematicin a number of ways. For example, dyes and pigments and their associatedchemistries for fabrication and incorporation into finished goods maynot be environmentally friendly.

BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments of the present disclosure will be more readilyappreciated upon review of the detailed description of its variousembodiments, described below, when taken in conjunction with theaccompanying drawings.

FIGS. 1A-1M illustrate footwear, apparel, athletic equipment,containers, electronic equipment, and vision wear that include theoptical elements of the present disclosure.

FIGS. 2A-2B illustrate side views of exemplary optical elements of thepresent disclosure.

DESCRIPTION

The present disclosure provides for articles that exhibit structuralcolors through the use of optical elements, where structural colors arevisible colors produced, at least in part, through optical effects(e.g., through scattering, refraction, reflection, interference, and/ordiffraction of visible wavelengths of light). The structural colorimparts an aesthetically appealing color to the article withoutrequiring the use of inks or pigments and the environmental impactassociated with their use.

The optical element can be used alone or optionally in combination witha textured surface), a primer layer, or both to impart the structuralcolor. The textured surface and/or the primer layer can be part of theoptical element or can be separate from the optical element, but, whenused with the optical element, impart the structural color. In otherwords, while the optical element alone can impart a first structuralcolor, the combination of the optical element with the textured surfaceor primer layer or both impart a first structural color. In someexamples, the second structural color is the same as the secondstructural color. Alternatively, the second structural color can differfrom the first structural color optical element based on a colorparameter such as hue, lightness, or iridescence type. In such cases,the combination of the optical element and the textured surface and/orthe primer layer impart the structural color to the article.

After disposing the optical element to the article, the article exhibitsa different color from the underlying surface of the article, withoutthe application of additional pigments or dyes to the article. Forexample, the structural color can differ from the color of theunderlying surface of the article based on a color parameter such ashue, lightness, iridescence type, or any combination thereof. Inparticular examples, the structural color and the color of theunderlying surface of the article differ both in hue and iridescencetype, where the structural color is iridescent (e.g., exhibits two ormore different hues when viewed from at least two different angles 15degrees apart), and the color of the underlying surface is notiridescent. The optical element can be disposed (e.g., affixed,attached, adhered, bonded, joined) to a surface of one or morecomponents of the footwear, such as on the shoe upper and/or the sole.The optical element can be incorporated into the sole by incorporatingit into a cushioning element such as a bladder or a foam. The soleand/or upper can be designed so that one or more portions of thestructurally colored component are visible in the finished article, byincluding an opening, or a transparent component covering thestructurally colored component, and the like.

The present disclosure provides for an article comprising a componentforming at least a portion of an sole article, the component having afirst surface; and an optical element having a first side and a secondside opposing the first side, wherein the first side of the opticalelement, the second side of the optical element, or both impart astructural color, wherein the first side of the optical element or thesecond side of the optical element is disposed on the first surface ofthe component to impart a structural color on the component. In aparticular example, the article is an article of footwear, and thecomponent is a footwear component. The footwear component is understoodto refer to a unitary or compound component such as upper for an articleof footwear, a sole for an article of footwear, a combinationupper/outsole for an article of footwear, and the like. It also canrefer to a sub-component or an element of a compound component, such as,for example, a heel counter, a rand, a toe cap, a bladder, a portion offoam, a lacing eyestay reinforcement, a tongue, a vamp, etc. The opticalelement can include one or more optical layers. A textured surfaceand/or a primer layer in combination with the optical element can impartthe structural color. The footwear component can be an upper or a soleor both. When the footwear component is a sole, it can be a cushioningelement sole, such as a bladder or a foam element.

While in many examples of this disclosure, a highly iridescentstructural color (e.g., a color which shifts over a wide range of hueswhen viewed from different angles) can be obtained, in other examples astructural color which does not shift over a wide range of hues whenviewed from different angles (e.g., a structural color which does notshift hues, or which shifts over a limited number of hues depending uponthe viewing angle) also can be obtained.

In one example, the present disclosure provides for the optical element,as disposed on a surface of a component, when measured according to theCIE 1976 color space under a given illumination condition at threeobservation angles between −15 degrees and +60 degrees, has a firstcolor measurement at a first angle of observation having coordinates L₁*and a₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b_(2*), and a third colormeasurement at a third angle of observation having coordinates L₃* anda₃* and b_(3*), wherein the L₁*, L_(2*), and L₃* values may be the sameor different, wherein the a₁*, a_(2*), and a₃* coordinate values may bethe same or different, wherein the b₁*, b_(2*), and b₃* coordinatevalues may be the same or different, and wherein the range of thecombined a₁*, a₂* and a₃* values is less than about 40% of the overallscale of possible a* values.

In another example, the present disclosure provides for the opticalelement, as disposed on a surface of a component, when measuredaccording to the CIE 1976 color space under a given illuminationcondition at two observation angles between −15 degrees and +60 degrees,has a first color measurement at a first angle of observation havingcoordinates L₁* and a₁* and b₁*, and a second color measurement at asecond angle of observation having coordinates L₂* and a₂* and b_(2*),wherein the L₁* and L₂* values may be the same or different, wherein thea₁* and a₂* coordinate values may be the same or different, wherein theb₁* and b₂* coordinate values may be the same or different, and whereinthe ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 100, whereΔE*_(ab)=[(L₁*-L₂*)²+(a₁*-a₂*)²+(b₁*-b₂*)²]^(1/2).

In yet another example, the present disclosure provides for the opticalelement, as disposed on a surface of a component, when measuredaccording to the CIELCH color space under a given illumination conditionat three observation angles between −15 degrees and +60 degrees, has afirst color measurement at a first angle of observation havingcoordinates L₁* and C₁* and h₁°, and a second color measurement at asecond angle of observation having coordinates L₂* and C₂* and h₂°, anda third color measurement at a third angle of observation havingcoordinates L₃* and C₃* and h₃°, wherein the L₁*, L_(2*), and L₃* valuesmay be the same or different, wherein the C₁*, C₂*, and C₃* coordinatevalues may be the same or different, wherein the h₁°, h₂° and h₃°coordinate values may be the same or different, and wherein the range ofthe combined h₁°, h₂° and h₃° values is less than about 60 degrees.

Now having described embodiments of the present disclosure generally,additional discussion regarding embodiments will be described in greaterdetails.

This disclosure is not limited to particular embodiments described, andas such may, of course, vary. The terminology used herein serves thepurpose of describing particular embodiments only, and is not intendedto be limiting, since the scope of the present disclosure will belimited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

The present disclosure provides for articles that exhibit structuralcolor. The structural color can be produced using an optical element,incorporated onto one or more components of the article, for example,when the article is an article of footwear, on an upper or sole of anarticle of footwear. The optical element can be incorporated into anarticle, for example, on an externally-facing surface of a component ofthe article. In the example where the article is an article of footwear,the externally-facing surface can be the shoe upper or the sole. Theoptical element can be incorporated with a cushioning element (e.g.,bladder, foam), which can be incorporated into a component that can beaffixed to the article optionally with other components to form thearticle. The article and/or component can be designed so that one ormore portions including the optical element are visible in the finishedarticle. For example, the portion including the optical element can beviewed through an opening, or through a transparent area or the like.

The article can be an article of footwear. The article of footwear canbe designed for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. Primarily, the article offootwear is intended for outdoor use on unpaved surfaces (in part or inwhole), such as on a ground surface including one or more of grass,turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether asan athletic performance surface or as a general outdoor surface.However, the article of footwear may also be desirable for indoorapplications, such as indoor sports including dirt playing surfaces forexample (e.g., indoor baseball fields with dirt infields).

The article of footwear can be designed for use in indoor or outdoorsporting activities, such as global football/soccer, golf, Americanfootball, rugby, baseball, running, track and field, cycling (e.g., roadcycling and mountain biking), and the like. The article of footwear canoptionally include traction elements (e.g., lugs, cleats, studs, andspikes as well as tread patterns) to provide traction on soft andslippery surfaces, where components of the present disclosure can beused or applied between or among the traction elements and optionally onthe sides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

The article can be an article of apparel (i.e., a garment). The articleof apparel can be an article of apparel designed for athletic or leisureactivities. The article of apparel can be an article of apparel designedto provide protection from the elements (e.g., wind and/or rain), orfrom impacts.

The article can be an article of sporting equipment. The article ofsporting equipment can be designed for use in indoor or outdoor sportingactivities, such as global football/soccer, golf, American football,rugby, baseball, running, track and field, cycling (e.g., road cyclingand mountain biking), and the like.

FIGS. 1A-M illustrate articles that include the optical element of thepresent disclosure. The optical element is represented by hashed areas12A′/12M′-12A″/12M″. The location of the optical element is providedonly to indicate one possible area that the optical element can belocated. Also, two locations are illustrated in the figures, but this isdone only for illustration purposes as the articles can include one or aplurality of optical elements, where the size and location can bedetermined based on the article. The optical element(s) located on eacharticle can represent a number, letter, symbol, design, emblem, graphicmark, icon, logo, or the like.

Articles of the present disclosure include the optical element that hasthe characteristic of imparting optical effects including structuralcolor. The optical element includes at least one optical layer (e.g., amultilayer reflector or a multilayer filter) optionally in combinationwith a textured surface (e.g., integral to the optical element or aspart of the surface of the article), optionally with a primer layer,optionally with a protective layer, or optionally with any combinationof the textured surface, the primer layer, and the protective layer. Theoptical element or the combination of the optical element optionallywith the textured surface and/or primer layer impart structural color(e.g., single color, multicolor, iridescent), to the article. Followingdisposing of the optical element on the article, the article appears tobe colored (i.e., to have a new, different color (e.g., a color whichdiffers in hue or iridescence or as otherwise described herein) than thecolor the surface of the article had prior to the disposing) without theapplication of additional pigments or dyes to the article. However,pigments and/or dyes can be used in conjunction with the optical elementto produce aesthetically pleasing effects.

As has been described herein, the structural color can include one of anumber of colors. The “color” of an article as perceived by a viewer candiffer from the actual color of the article, as the color perceived by aviewer is determined by the actual color of the article by the presenceof optical elements which may absorb, refract, interfere with, orotherwise alter light reflected by the article, by the viewer's abilityto detect the wavelengths of light reflected by the article, by thewavelengths of light used to illuminate the article, as well as otherfactors such as the coloration of the environment of the article, andthe type of incident light (e.g., sunlight, fluorescent light, and thelike). As a result, the color of an object as perceived by a viewer candiffer from the actual color of the article.

Conventionally, color is imparted to man-made objects by applyingcolored pigments or dyes to the object. More recently, methods ofimparting “structural color” to man-made objects have been developed.Structural color is color which is produced, at least in part, bymicroscopically structured surfaces that interfere with visible lightcontacting the surface. The structural color is color caused by physicalphenomena including the scattering, refraction, reflection,interference, and/or diffraction of light, unlike color caused by theabsorption or emission of visible light through coloring matters. Forexample, optical phenomena which impart structural color can includemultilayer interference, thin-film interference, refraction, dispersion,light scattering, Mie scattering, diffraction, and diffraction grating.In various aspects described herein, structural color imparted to anarticle can be visible to a viewer having 20/20 visual acuity and normalcolor vision from a distance of about 1 meter from the article.

As described herein, structural color is produced, at least in part, bythe optical element, as opposed to the color being produced solely bypigments and/or dyes. The coloration of a structurally-colored articlecan be due solely to structural color (i.e., the article, a coloredportion of the article, or a colored outer layer of the article can besubstantially free of pigments and/or dyes). Structural color can alsobe used in combination with pigments and/or dyes, for example, to alterall or a portion of a structural color.

“Hue” is commonly used to describe the property of color which isdiscernible based on a dominant wavelength of visible light, and isoften described using terms such as magenta, red, orange, yellow, green,cyan, blue, indigo, violet, etc. or can be described in relation (e.g.,as similar or dissimilar) to one of these. The hue of a color isgenerally considered to be independent of the intensity or lightness ofthe color. For example, in the Munsell color system, the properties ofcolor include hue, value (lightness) and chroma (color purity).Particular hues are commonly associated with particular ranges ofwavelengths in the visible spectrum: wavelengths in the range of about700 to 635 nanometers are associated with red, the range of about 635 to590 nanometers is associated with orange, the range of about 590 to 560nanometers is associated with yellow, the range of about 560 to 520nanometers is associated with green, the range of about 520 to 490nanometers is associated with cyan, the range of about 490 nanometers to450 nanometers is associated with blue, and the range of about 450 to400 nanometers is associated with violet.

The color (including the hue) of an article as perceived by a viewer candiffer from the actual color of the article. The color as perceived by aviewer depends not only on the physics of the article, but also itsenvironment, and the characteristics of the perceiving eye and brain.For example, as the color perceived by a viewer is determined by theactual color of the article (e.g., the color of the light leaving thesurface of the article), by the viewer's ability to detect thewavelengths of light reflected or emitted by the article, by thewavelengths of light used to illuminate the article, as well as otherfactors such as the coloration of the environment of the article, andthe type of incident light (e.g., sunlight, fluorescent light, and thelike). As a result, the color of an object as perceived by a viewer candiffer from the actual color of the article.

When used in the context of structural color, one can characterize thehue of a structurally-colored article, i.e., an article that has beenstructurally colored by incorporating an optical element into thearticle, based on the wavelengths of light the structurally-coloredportion of the article absorbs and reflects (e.g., linearly andnon-linearly). While the optical element may impart a first structuralcolor, the presence of an optional textured surface and/or primer layercan alter the structural color. Other factors such as coatings ortransparent elements may further alter the perceived structural color.The hue of the structurally colored article can include any of the huesdescribed herein as well as any other hues or combination of hues. Thestructural color can be referred to as a “single hue” (i.e., the hueremains substantially the same, regardless of the angle of observationand/or illumination), or “multihued” (i.e., the hue varies dependingupon the angle of observation and/or illumination). The multihuedstructural color can be iridescent (i.e., the hue changes gradually overtwo or more hues as the angle of observation or illumination changes).The hue of an iridescent multihued structural color can change graduallyacross all the hues in the visible spectrum (e.g., like a “rainbow”) asthe angle of observation or illumination changes. The hue of aniridescent multihued structural color can change gradually across alimited number of hues in the visible spectrum as the angle ofobservation or illumination changes, in other words, one or more hues inthe visible spectrum (e.g., red, orange, yellow, etc.) are not observedin the structural color as the angle of observation or illuminationchanges. Only one hue, or substantially one hue, in the visible spectrummay be present for a single-hued structural color. The hue of amultihued structural color can change more abruptly between a limitednumber of hues (e.g., between 2-8 hues, or between 2-4 hues, or between2 hues) as the angle of observation or illumination changes.

The structural color can be a multi-hued structural color in which twoor more hues are imparted by the structural color.

The structural color can be iridescent multi-hued structural color inwhich the hue of the structural color varies over a wide number of hues(e.g., 4, 5, 6, 7, 8 or more hues) when viewed at a single viewingangle, or when viewed from two or more different viewing angles that areat least 15 degrees apart from each other.

The structural color can be limited iridescent multi-hue structuralcolor in which the hue of the structural color varies, or variessubstantially (e.g., about 90 percent, about 95 percent, or about 99percent) over a limited number of hues (e.g., 2 hues, or 3 hues) whenviewed from two or more different viewing angles that are at least 15degrees apart from each other. In some aspects, a structural colorhaving limited iridescence is limited to two, three or four huesselected from the RYB primary colors of red, yellow and blue, optionallythe RYB primary and secondary colors of red, yellow, blue, green, orangeand purple, or optionally the RYB primary, secondary and tertiary colorsof red, yellow, blue, green, orange purple, green-yellow, yellow-orange,orange-red, red-purple, purple-blue, and blue-green.

The structural color can be single-hue angle-independent structuralcolor in which the hue, the hue and value, or the hue, value and chromaof the structural color is independent of or substantially (e.g., about90 percent, about 95 percent, or about 99 percent) independent of theangle of observation. For example, the single-hue angle-independentstructural color can display the same hue or substantially the same huewhen viewed from at least 3 different angles that are at least 15degrees apart from each other (e.g., single-hue structural color).

The structural color imparted can be a structural color having limitediridescence such that, when each color observed at each possible angleof observation is assigned to a single hue selected from the groupconsisting of the primary, secondary and tertiary colors on the redyellow blue (RYB) color wheel, for a single structural color, all of theassigned hues fall into a single hue group, wherein the single hue groupis one of a) green-yellow, yellow, and yellow-orange; b) yellow,yellow-orange and orange; c) yellow-orange, orange, and orange-red; d)orange-red, and red-purple; e) red, red-purple, and purple; f)red-purple, purple, and purple-blue; g) purple, purple-blue, and blue;h) purple-blue, blue, and blue-green; i) blue, blue-green and green; andj) blue-green, green, and green-yellow. In other words, in this exampleof limited iridescence, the hue (or the hue and the value, or the hue,value and chroma) imparted by the structural color varies depending uponthe angle at which the structural color is observed, but the hues ofeach of the different colors viewed at the various angles ofobservations varies over a limited number of possible hues. The huevisible at each angle of observation can be assigned to a singleprimary, secondary or tertiary hue on the red yellow blue (RYB) colorwheel (i.e., the group of hues consisting of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green). For example, while a plurality ofdifferent colors are observed as the angle of observation is shifted,when each observed hue is classified as one of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green, the list of assigned hues includes no morethan one, two, or three hues selected from the list of RYB primary,secondary and tertiary hues. In some examples of limited iridescence,all of the assigned hues fall into a single hue group selected from huegroups a)-j), each of which include three adjacent hues on the RYBprimary, secondary and tertiary color wheel. For example, all of theassigned hues can be a single hue within hue group h) (e.g., blue), orsome of the assigned hues can represent two hues in hue group h) (e.g.,purple-blue and blue), or can represent three hues in hue group h)(e.g., purple-blue, blue, and blue-green).

Similarly, other properties of the structural color, such as thelightness of the color, the saturation of the color, and the purity ofthe color, among others, can be substantially the same regardless of theangle of observation or illumination, or can vary depending upon theangle of observation or illumination. The structural color can have amatte appearance, a glossy appearance, or a metallic appearance, or acombination thereof.

As discussed above, the color (including hue) of a structurally-coloredarticle can vary depending upon the angle at which thestructurally-colored article is observed or illuminated. The hue or huesof an article can be determined by observing the article, orilluminating the article, at a variety of angles using constant lightingconditions. As used herein, the “angle” of illumination or viewing isthe angle measured from an axis or plane that is orthogonal to thesurface. The viewing or illuminating angles can be set between about 0and 180 degrees. The viewing or illuminating angles can be set at 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15 degreesand the color can be measured using a colorimeter or spectrophotometer(e.g., Konica Minolta), which focuses on a particular area of thearticle to measure the color. The viewing or illuminating angles can beset at 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75degrees, 90 degrees, 105 degrees, 120 degrees, 135 degrees, 150 degrees,165 degrees, 180 degrees, 195 degrees, 210 degrees, 225 degrees, 240degrees, 255 degrees, 270 degrees, 285 degrees, 300 degrees, 315degrees, 330 degrees, and 345 degrees and the color can be measuredusing a colorimeter or spectrophotometer. In a particular example of amultihued article colored using only structural color, when measured at0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees, the hues measured for article consisted of “blue” at three ofthe measurement angles, “blue-green” at 2 of the measurement angles and“purple” at one of the measurement angles.

In other embodiments, the color (including hue, value and/or chroma) ofa structurally-colored article does not change substantially, if at all,depending upon the angle at which the article is observed orilluminated. In instances such as this the structural color can be anangle-independent structural color in that the hue, the hue and value,or the hue, value and chroma observed is substantially independent or isindependent of the angle of observation.

Various methodologies for defining color coordinate systems exist. Oneexample is L*a*b* color space, where, for a given illuminationcondition, L* is a value for lightness, and a* and b* are values forcolor-opponent dimensions based on the CIE coordinates (CIE 1976 colorspace or CIELAB). In an embodiment, a structurally-colored articlehaving structural color can be considered as having a “single” colorwhen the change in color measured for the article is within about 10% orwithin about 5% of the total scale of the a* or b* coordinate of theL*a*b* scale (CIE 1976 color space) at three or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees. In certain embodiments, colors which, whenmeasured and assigned values in the L*a*b* system that differ by atleast 5 percent of the scale of the a* and b* coordinates, or by atleast 10 percent of the scale of the a* and b* coordinates, areconsidered to be different colors. The structurally-colored article canhave a change of less than about 40%, or less than about 30%, or lessthan about 20%, or less than about 10%, of the total scale of the a*coordinate or b* coordinate of the L*a*b* scale (CIE 1976 color space)at three or more measured observation or illumination angles.

A change in color between two measurements in the CIELAB space can bedetermined mathematically. For example, a first measurement hascoordinates L₁*, a₁* and b₁*, and a second measurement has coordinatesL_(2*), a₂* and b_(2*). The total difference between these twomeasurements on the CIELAB scale can be expressed as ΔE*_(ab), which iscalculated as follows:ΔE*_(ab)=[(L₁*-L₂*)²+(a₁*-a₂*)²+(b₁*-b₂*)²]^(1/2). Generally speaking,if two colors have a ΔE*_(ab) of less than or equal to 1, the differencein color is not perceptible to human eyes, and if two colors have aΔE*_(ab) of greater than 100 the colors are considered to be oppositecolors, while a ΔE*_(ab) of about 2-3 is considered the threshold forperceivable color difference. In certain embodiments, a structurallycolored article having structural color can be considered as having a“single” color when the ΔE*_(ab) is less than 60, or less than 50, orless than 40, or less than 30, between three or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees. The structurally-colored article can have aΔE*_(ab) that is less than about 100, or less than about 80, or lessthan about 60, between two or more measured observation or illuminationangles.

Another example of a color scale is the CIELCH color space, where, for agiven illumination condition, L* is a value for lightness, C* is a valuefor chroma, and h° denotes a hue as an angular measurement. In anembodiment, a structurally-colored article having structural color canbe considered as having a “single” color when the color measured for thearticle is less than 10 degrees different or less than 5 degreesdifferent at the h° angular coordinate of the CIELCH color space, atthree or more measured observation or illumination angles selected frommeasured at observation or illumination angles of 0 degrees, 15 degrees,30 degrees, 45 degrees, 60 degrees, and −15 degrees. In certainembodiments, colors which, when measured and assigned values in theCIELCH system that vary by at least 45 degrees in the h° measurements,are considered to be different colors The structurally-colored articlecan have a change of less than about 60 degrees, or less than about 50degrees, or less than about 40 degrees, or less than about 30 degrees,or less than about 20 degrees, or less than about 10 degrees, in the h°measurements of the CIELCH system at three or more measured observationor illumination angles.

Another system for characterizing color includes the “PANTONE” MatchingSystem (Pantone LLC, Carlstadt, New Jersey, USA), which provides avisual color standard system to provide an accurate method forselecting, specifying, broadcasting, and matching colors through anymedium. In an example, a structurally-colored article having astructural color can be considered as having a “single” color when thecolor measured for the article is within a certain number of adjacentstandards, e.g., within 20 adjacent PANTONE standards, at three or moremeasured observation or illumination angles selected from 0 degrees, 15degrees, 30 degrees, 45 degrees, 60 degrees, and −15 degrees.

Now having described color, additional details regarding the opticalelement are provided. As described herein, the article includes theoptical element. The optical element can include at least one opticallayer. The optical element can be or include a single or multilayerreflector or a multilayer filter. The optical element can function tomodify the light that impinges thereupon so that structural color isimparted to the article. The optical element can include at least oneoptical layer and optionally one or more additional layers (e.g., aprotective layer, the textured layer, the primer layer, a polymer layer,and the like).

The method of making the structurally colored article can includedisposing (e.g., affixing, attaching, bonding, fastening, joining,appending, connecting, binding and includes operably disposing etc.) theoptical element onto an article (e.g., an article of footwear, anarticle of apparel, an article of sporting equipment, etc.). The articleincludes a component, and the component has a surface upon which theoptical element can be disposed. The surface of the article can be madeof a material such as a thermoplastic material or thermoset material, asdescribed herein. For example, the article has a surface including athermoplastic material (i.e., a first thermoplastic material), forexample an externally-facing surface of the component or aninternally-facing surface of the component (e.g., an externally-facingsurface or an internally-facing surface a bladder). The optical elementcan be disposed onto the thermoplastic material, for example.

The optical element has a first side (including the outer surface) and asecond side opposing the first side (including the opposing outersurface), where the first side or the second side is adjacent thearticle. For example, when the optical element is used in conjunctionwith a component having internally-facing and externally-facingsurfaces, such as a film or a bladder, the first side of the opticalelement can be disposed on the internally-facing surface of thecomponent, such as in the following order: second side of the opticalelement/core of the optical element/first side of the opticalelement/internally-facing surface of the component/core of thecomponent/externally-facing surface of the component. Alternatively, thesecond side the optical element can be disposed on the internally-facingsurface of the component, such as in the following order: first side ofthe optical element/core of the optical element/second side of theoptical element/internally-facing surface of the component/core of thecomponent wall/externally-facing surface of the component. In anotherexample, the first side of the optical element can be disposed on theexternally-facing surface of the component, such as in the followingorder: internally-facing surface of the component/core of thecomponent/externally-facing surface of the component/first side of theoptical element/core of the optical element/second side of the opticalelement. Similarly, the second side of the optical element can bedisposed on the externally-facing surface of the component, such as inthe following order: internally-facing surface of the component/core ofthe component/externally-facing surface of the component/second side ofthe optical element/core of the optical element/first side of theoptical element. In examples where the optional textured surface, theoptional primer layer, or both are present, the textured surface and/orthe primer layer can be located at the interface between the surface ofthe component and a side of the optical element.

The optical element or layers or portions thereof (e.g., optical layer)can be formed using known techniques such as physical vapor deposition,electron beam deposition, atomic layer deposition, molecular beamepitaxy, cathodic arc deposition, pulsed laser deposition, sputteringdeposition (e.g., radio frequency, direct current, reactive,non-reactive), chemical vapor deposition, plasma-enhanced chemical vapordeposition, low pressure chemical vapor deposition and wet chemistrytechniques such as layer-by-layer deposition, sol-gel deposition,Langmuir blodgett, and the like. The temperature of the first side canbe adjusted using the technique to form the optical element and/or aseparate system to adjust the temperature. Additional details areprovided herein.

The optical layer(s) of the optical element can comprise a multilayerreflector. The multilayer reflector can be configured to have a certainreflectivity at a given wavelength of light (or range of wavelengths)depending, at least in part, on the material selection, thickness andnumber of the layers of the multilayer reflector. In other words, onecan carefully select the materials, thicknesses, and numbers of thelayers of a multilayer reflector and optionally its interaction with oneor more other layers, so that it can reflect a certain wavelength oflight (or range of wavelengths), to produce a desired structural color.The optical layer can include at least two adjacent layers, where theadjacent layers have different refractive indices. The difference in theindex of refraction of adjacent layers of the optical layer can be about0.0001 to 50 percent, about 0.1 to 40 percent, about 0.1 to 30 percent,about 0.1 to 20 percent, about 0.1 to 10 percent (and other ranges therebetween (e.g., the ranges can be in increments of 0.0001 to 5 percent)).The index of refraction depends at least in part upon the material ofthe optical layer and can range from 1.3 to 2.6.

The optical layer can include 2 to 20 layers, 2 to 10 layer, 2 to 6layers, or 2 to 4 layers. Each layer of the optical layer can have athickness that is about one-fourth of the wavelength of light to bereflected to produce the desired structural color. Each layer of theoptical layer can have a thickness of about 10 to 500 nanometers orabout 90 to 200 nanometers. The optical layer can have at least twolayers, where adjacent layers have different thicknesses and optionallythe same or different refractive indices.

The optical element can comprise a multilayer filter. The multilayerfilter destructively interferes with light that impinges upon thestructure or article, where the destructive interference of the lightand optionally interaction with one or more other layers or structures(e.g., a multilayer reflector, a textured structure) impart thestructural color. In this regard, the layers of the multilayer filtercan be designed (e.g., material selection, thickness, number of layer,and the like) so that a single wavelength of light, or a particularrange of wavelengths of light, make up the structural color. Forexample, the range of wavelengths of light can be limited to a rangewithin plus or minus 30 percent of a single wavelength, or within plusor minus 20 percent of a single wavelength, or within plus or minus 10percent of a single wavelength, or within plus or minus 5 percent of asingle wavelength. The range of wavelengths can be broader to produce amore iridescent structural color.

The optical layer(s) can include multiple layers where each layerindependently comprises a material selected from: the transition metals,the metalloids, the lanthanides, and the actinides, as well as nitrides,oxynitrides, sulfides, sulfates, selenides, and tellurides of these. Thematerial can be selected to provide an index of refraction that whenoptionally combined with the other layers of the optical elementachieves the desired result. One or more layers of the optical layer canbe made of liquid crystals. Each layer of the optical layer can be madeof liquid crystals. One or more layers of the optical layer can be madeof a material such as: silicon dioxide, titanium dioxide, zinc sulfide,magnesium fluoride, tantalum pentoxide, aluminum oxide, or a combinationthereof. Each layer of the optical layer can be made of a material suchas: silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride,tantalum pentoxide, aluminum oxide, or a combination thereof.

The optical element can be uncolored (e.g., no pigments or dyes added tothe structure or its layers), colored (e.g., pigments and/or dyes areadded to the structure or its layers (e.g., dark or black color)),reflective, and/or transparent (e.g., percent transmittance of 75percent or more). The surface of the component upon which the opticalelement is disposed can be uncolored (e.g., no pigments or dyes added tothe material), colored (e.g., pigments and/or dyes are added to thematerial (e.g., dark or black color)), reflective, and/or transparent(e.g., percent transmittance of 75 percent or more).

The optical layer(s) can be formed in a layer-by-layer manner, whereeach layer has a different index of refraction. Each layer of theoptical layer can be formed using known techniques such as physicalvapor deposition including: chemical vapor deposition, pulsed laserdeposition, evaporative deposition, sputtering deposition (e.g., radiofrequency, direct current, reactive, non-reactive), plasma enhancedchemical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett and thelike.

As mentioned above, the optical element can include one or more layersin addition to the optical layer(s). The optical element has a firstside (e.g., the side having a surface) and a second side (e.g., the sidehaving a surface), where the first side or the second side is adjacentthe surface of the component. The one or more other layers of theoptical element can be on the first side and/or the second side of theoptical element. For example, the optical element can include aprotective layer and/or a polymeric layer such as a thermoplasticpolymeric layer, where the protective layer and/or the polymeric layercan be on one or both of the first side and the second side of theoptical element. In another example, the optical element can include aprimer layer as described herein. One or more of the optional otherlayers can include a textured surface. Alternatively or in addition, oneor more optical layers of the optical element can include a texturedsurface.

A protective layer can be disposed on the first and/or second side ofthe optical layer to protect the optical layer. The protective layer ismore durable or more abrasion resistant than the optical layer. Theprotective layer is optically transparent to visible light. Theprotective layer can be on the first side of the optical element toprotect the optical layer. All or a portion of the protective layer caninclude a dye or pigment in order to alter an appearance of thestructural color. The protective layer can include silicon dioxide,glass, combinations of metal oxides, or mixtures of polymers. Theprotective layer can have a thickness of about 3 nanometers to 1millimeter.

The protective layer can be formed using physical vapor deposition,chemical vapor deposition, pulsed laser deposition, evaporativedeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), plasma enhanced chemical vapordeposition, electron beam deposition, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett, andthe like. Alternatively or in addition, the protective layer can beapplied by spray coating, dip coating, brushing, spin coating, doctorblade coating, and the like.

A polymeric layer can be disposed on the first and/or the second side ofthe optical element. The polymeric layer can be used to dispose theoptical element onto an article, such as, for example, when the articledoes not include a thermoplastic material to adhere the optical element.The polymeric layer can comprise a polymeric adhesive material, such asa hot melt adhesive. The polymeric layer can be a thermoplastic materialand can include one or more layers. The thermoplastic material can beany one of the thermoplastic material described herein. The polymericlayer can be applied using various methodologies, such as spin coating,dip coating, doctor blade coating, and so on. The polymeric layer canhave a thickness of about 3 nanometer to 1 millimeter.

As described above, one or more embodiments of the present disclosureprovide articles that incorporate the optical element (e.g., single ormultilayer structures) on a side of a component of the article to impartstructural color. The optical element can be disposed onto thethermoplastic material of the side of the article, and the side of thearticle can include a textile, including a textile comprising thethermoplastic material.

Having described the structural color structure, additional details willnow be described for the optional textured surface. As described herein,the component includes the optical element and the optical element caninclude at least one optical layer and optionally a textured surface.The textured surface can be a surface of a textured structure or atextured layer. The textured surface may be provided as part of theoptical element. For example, the optical element may comprise atextured layer or a textured structure that comprises the texturedsurface. The textured surface may be formed on the first or second sideof the optical element. For example, a side of the optical layer may beformed or modified to provide a textured surface, or a textured layer ortextured structure can be affixed to the first or second side of theoptical element. The textured surface may be provided as part of thecomponent to which the optical element is disposed. For example, theoptical element may be disposed onto the surface of the component wherethe surface of the component is a textured surface, or the surface ofthe component includes a textured structure or a textured layer affixedto it.

The textured surface (or a textured structure or textured layerincluding the textured surface) may be provided as a feature on or partof another medium, such as a transfer medium, and imparted to a side orlayer of the optical element or to the surface of the component. Forexample, a mirror image or relief form of the textured surface may beprovided on the side of a transfer medium, and the transfer mediumcontacts a side of the optical element or the surface of the componentin a way that imparts the textured surface to the optical element orarticle. While the various embodiments herein may be described withrespect to a textured surface of the optical element, it will beunderstood that the features of the textured surface, or a texturedstructure or textured layer, may be imparted in any of these ways.

The textured surface can contribute to the structural color resultingfrom the optical element. As described herein, structural coloration isimparted, at least in part, due to optical effects caused by physicalphenomena such as scattering, diffraction, reflection, interference orunequal refraction of light rays from an optical element. The texturedsurface (or its mirror image or relief) can include a plurality ofprofile features and flat or planar areas. The plurality of profilefeatures included in the textured surface, including their size, shape,orientation, spatial arrangement, etc., can affect the light scattering,diffraction, reflection, interference and/or refraction resulting fromthe optical element. The flat or planar areas included in the texturedsurface, including their size, shape, orientation, spatial arrangement,etc., can affect the light scattering, diffraction, reflection,interference and/or refraction resulting from the optical element. Thedesired structural color can be designed, at least in part, by adjustingone or more of properties of the profile features and/or flat or planarareas of the textured surface.

The profile features can extend from a side of the flat areas, so as toprovide the appearance of projections and/or depressions therein. In anaspect, the flat area can be a flat planar area. A profile feature mayinclude various combinations of projections and depressions. Forexample, a profile feature may include a projection with one or moredepressions therein, a depression with one or more projections therein,a projection with one or more further projections thereon, a depressionwith one or more further depressions therein, and the like. The flatareas do not have to be completely flat and can include texture,roughness, and the like. The texture of the flat areas may notcontribute much, if any, to the imparted structural color. The textureof the flat areas typically contributes to the imparted structuralcolor. For clarity, the profile features and flat areas are described inreference to the profile features extending above the flat areas, butthe inverse (e.g., dimensions, shapes, and the like) can apply when theprofile features are depressions in the textured surface.

The textured surface can comprise a thermoplastic material. The profilefeatures and the flat areas can be formed using a thermoplasticmaterial. For example, when the thermoplastic material is heated aboveits softening temperature a textured surface can be formed in thethermoplastic material such as by molding, stamping, printing,compressing, cutting, etching, vacuum forming, etc., the thermoplasticmaterial to form profile features and flat areas therein. The texturedsurface can be imparted on a side of a thermoplastic material. Thetextured surface can be formed in a layer of thermoplastic material. Theprofile features and the flat areas can be made of the samethermoplastic material or a different thermoplastic material.

The textured surface generally has a length dimension extending along anx-axis, and a width dimension extending along a z-axis, and a thicknessdimension extending along a y-axis. The textured surface has a generallyplanar portion extending in a first plane that extends along the x-axisand the z-axis. A profile feature can extend outward from the firstplane, so as to extend above or below the plane x. A profile feature mayextend generally orthogonal to the first plane, or at an angle greaterto or less than 90 degrees to the first plane.

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. A textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers. The profile feature can have dimensions in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. All of the dimensions of the profile feature (e.g., length,width, height, diameter, depending on the geometry) can be in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. The textured surface can have a plurality of profilefeatures having dimensions that are 1 micrometer or less. In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have a dimension inthis range. The profile features can have a ratio of width:height and/orlength:height dimensions of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5and 1:10.

The textured surface can have a profile feature and/or flat area with adimension within the micrometer range of dimensions. A textured surfacecan have a profile feature and/or flat area with a dimension of about 1micrometer to about 500 micrometers. All of the dimensions of theprofile feature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, e.g., from about 1 micrometerto about 500 micrometers. The textured surface can have a plurality ofprofile features having dimensions that are from about 1 micrometer toabout 500 micrometer. In this context, the phrase “plurality of theprofile features” is meant to mean that about 50 percent or more, about60 percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have a dimension in this range. The height of the profilefeatures (or depth if depressions) can be about 0.1 and 50 micrometers,about 1 to 5 micrometers, or 2 to 3 micrometers. The profile featurescan have a ratio of width:height and/or length:height dimensions ofabout 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1:10.

A textured surface can have a plurality of profile features having amixture of size dimensions within the nanometer to micrometer range(e.g., a portion of the profile features are on the nanometer scale anda portion of the profile features are on the micrometer scale). Atextured surface can have a plurality of profile features having amixture of dimensional ratios. The textured surface can have a profilefeature having one or more nanometer-scale projections or depressions ona micrometer-scale projection or depression.

The profile feature can have height and width dimensions that are withina factor of three of each other (0.33w≤h≤3w where w is the width and his the height of the profile feature) and/or height and lengthdimensions that are within a factor of three of each other (0.33l≤h≤3lwhere l is the length and h is the height of the profile feature). Theprofile feature can have a ratio of length:width that is from about 1:3to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1,or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of theprofile features can be substantially the same or different.

The profile features can have a certain spatial arrangement. The spatialarrangement of the profile features may be uniform, such as spacedevenly apart or forming a pattern. The spatial arrangement can berandom. Adjacent profile features can be about 1 to 100 micrometersapart or about 5 to 100 micrometers apart. The desired spacing candepend, at least in part, on the size and/or shape of the profilestructures and the desired structural color effect.

The profile features can have a certain cross-sectional shape (withrespect to a plane parallel the first plane). The textured surface canhave a plurality of profile features having the same or similarcross-sectional shape. The textured surface has a plurality of profilefeatures having a mixture of different cross-sectional shapes. Thecross-sectional shapes of the profile features can include polygonal(e.g., square or triangle or rectangle cross section), circular,semi-circular, tubular, oval, random, high and low aspect ratios,overlapping profile features, and the like.

The profile feature (e.g., about 10 nanometers to 500 micrometers) caninclude an upper, convexly curved surface. The curved surface may extendsymmetrically either side of an uppermost point.

The profile feature can include protrusions from the textured surface.The profile feature can include indents (hollow areas) formed in thetextured surface. The profile feature can have a smooth, curved shape(e.g., a polygonal cross-section with curved corners).

The profile features (whether protrusions or depressions) can beapproximately conical or frusto-conical (i.e. the projections or indentsmay have horizontally or diagonally flattened tops) or have anapproximately part-spherical surface (e.g., a convex or concave surfacerespectively having a substantially even radius of curvature).

The profile features may have one or more sides or edges that extend ina direction that forms an angle to the first plane of the texturedsurface. The angle between the first plane and a side or edge of theprofile feature is about 45 degrees or less, about 30 degrees or less,about 25 degrees or less, or about 20 degrees or less. The one or moresides or edges may extend in a linear or planar orientation, or may becurved so that the angle changes as a function of distance from thefirst plane. The profile features may have one or more sides thatinclude step(s) and/or flat side(s). The profile feature can have one ormore sides (or portions thereof) that can be orthogonal or perpendicularto the first plane of the textured surface, or extend at an angle ofabout 10 degrees to 89 degrees to the first plane (90 degrees beingperpendicular or orthogonal to the first plane)). The profile featurecan have a side with a stepped configuration, where portions of the sidecan be parallel to the first plane of the textured surface or have anangle of about 1 degrees to 179 degrees (0 degrees being parallel to thefirst plane)).

The textured surface can have profile features with varying shapes(e.g., the profile features can vary in shape, height, width and lengthamong the profile features) or profile features with substantiallyuniform shapes and/or dimensions. The structural color produced by thetextured surface can be determined, at least in part, by the shape,dimensions, spacing, and the like, of the profile features.

The profile features can be shaped so as to result in a portion of thesurface (e.g., about 25 to 50 percent or more) being about normal to theincoming light when the light is incident at the normal to the firstplane of the textured surface. The profile features can be shaped so asto result in a portion of the surface (e.g., about 25 to 50 percent ormore) being about normal to the incoming light when the light isincident at an angle of up to 45 degrees to the first plane of thetextured surface.

The spatial orientation of the profile features on the textured surfaceis set to reduce distortion effects, e.g., caused by the interference ofone profile feature with another in regard to the structural color ofthe structure. Since the shape, dimension, relative orientation of theprofile features can vary considerably across the textured surface, thedesired spacing and/or relative positioning for a particular area (e.g.,in the micrometer range or about 1 to 10 square micrometers) havingprofile features can be appropriately determined. As discussed herein,the shape, dimension, relative orientation of the profile featuresaffect the contours of the optical layer, so the dimensions (e.g.,thickness), index of refraction, number of layers in the optical layerare considered when designing the textured side of the texture layer.

The profile features are located in nearly random positions relative toone another across a specific area of the textured surface (e.g., in themicrometer range or about 1 to 10 square micrometers to centimeter rangeor about 0.5 to 5 square centimeters, and all range increments therein),where the randomness does not defeat the purpose of producing thestructural color. In other words, the randomness is consistent with thespacing, shape, dimension, and relative orientation of the profilefeatures, the dimensions (e.g., thickness), index of refraction, andnumber of layers in the optical layer, and the like, with the goal toachieve the structural color.

The profile features are positioned in a set manner relative to oneanother across a specific area of the textured surface to achieve thepurpose of producing the structural color. The relative positions of theprofile features do not necessarily follow a pattern, but can follow apattern consistent with the desired structural color. As mentioned aboveand herein, various parameters related to the profile features, flatareas, and optical layer can be used to position the profile features ina set manner relative to one another.

The textured surface can include micro and/or nanoscale profile featuresthat can form gratings (e.g., a diffractive grating), photonic crystalstructure, a selective mirror structure, crystal fiber structures,deformed matrix structures, spiraled coiled structures, surface gratingstructures, and combinations thereof. The textured surface can includemicro and/or nanoscale profile features that form a grating having aperiodic or non-periodic design structure to impart the structuralcolor. The micro and/or nanoscale profile features can have apeak-valley pattern of profile features and/or flat areas to produce thedesired structural color. The grading can be an Echelette grating.

The profile features and the flat areas of the textured surface in theoptical element can appear as topographical undulations in each layer ofthe optical layer. For example, referring to FIGS. 2A and 2B, an opticalelement 200 includes a textured structure 220 having a plurality ofprofile features 222 and flat areas 224. As described herein, one ormore of the profile features 222 can be projections from a surface ofthe textured structure 220 (as shown in FIG. 2A), and/or one or more ofthe profile features 222 can be depressions in a surface of the texturedstructure 220 (as shown in FIG. 2B). One or more optical layers 240 aredisposed on the side or surface of the textured structure 220 having theprofile features 222 and flat areas 224. In some embodiments, theresulting topography of the one or more optical layers 240 is notidentical to the topography of the textured structure 220, but rather,the one or more optical layers 240 can have elevated or depressedregions 242 which are either elevated or depressed relative to theheight of the planar regions 244 and which roughly correspond to thelocation of the profile features 222 of the textured structure 220. Theone or more optical layers 240 also have planar regions 244 that roughlycorrespond to the location of the flat areas 224 of the texturedstructure 220. Due to the presence of the elevated or depressed regions242 and the planar regions 244, the resultant overall topography of theoptical layer 240 can be that of an undulating or wave-like structure.The dimension, shape, and spacing of the profile features along with thenumber of layers of the optical layer, the thickness of each of thelayers, refractive index of each layer, and the type of material, can beused to produce an optical element which results in a particularstructural color.

Now having described the optical element and the textured surface,additional details will be provided for the optionally present primerlayer. The optical element is used to produce the structural color,where the structural color structure can include (e.g., as part of theoptical element) or use the primer layer to produce the structuralcolor. As described herein, the structural color structure can alsoinclude (e.g., as part of optical element) the optional texturedsurface, such as a texture layer and/or a textured structure. Thecombination of the optical element and the optional texture layer andthe optional primer layer can form a structural color structure havingone of the following designs: texture layer/primer layer/optical elementor primer layer/texture layer/optical element. The primer layer can havea thickness of about 3 nanometers to 200 micrometers, or about 1 toabout 200 micrometers, or about 10 to about 100 micrometers, or about 10to about 80 micrometers. The structural color structure can include thecombination of the primer layer, the optical element, and (optionally)textured surface. Selection of variables associated with the primerlayer, texture layer, and the optical element, can be used to controland select the desired structural color.

The structural color structure can include the primer layer, thetextured surface (optionally), and the optical element (e.g., opticallayer), where the optical element is disposed on the textured surface orthe primer layer, depending upon the design. The combination of theprimer layer, the textured surface, and the optical element impartsstructural color, to the article, where the structural color isdifferent than the primer color, optionally with or without theapplication of pigments or dyes to the article. The optical element canbe disposed onto the primer layer and/or the textured surface. Theprimer layer can include the textured surface as described herein. Forexample, the primer layer can be formed in a way so that it has thetextured surface.

The primer layer can include a paint layer (e.g., dyes, pigments, and acombination thereof), an ink layer, a reground layer, an at leastpartially degraded polymer layer, a metal layer, an oxide layer, or acombination thereof. The primer layer can have a light or dark color.The primer layer can have a dark color. For example the dark color canbe selected from: black, shades of black, brown, dark shades of brown,dark shades of red, dark shades of orange, dark shades of yellow, darkshades of green, dark shades of cyan, dark shades of blue, dark shadesof violet, grey, dark shades of gray, dark shades of magenta, darkshades of indigo, tones, tints, shades, or hues of any of these, and acombination thereof. The color can be defined using the L*a*b system,where the value of L* can be about 70 or less, about 60 or less, about50 or less, about 40 or less, or about 30 or less and a* and b*coordinate values can vary across the positive and negative valuescales.

The primer layer can be formed using digital printing, inkjet printing,offset printing, pad printing, screen printing, flexographic printing,heat transfer printing, physical vapor deposition including: chemicalvapor deposition, pulsed laser deposition, evaporative deposition,sputtering deposition (radio frequency, direct current, reactive,non-reactive), plasma enhanced chemical vapor deposition, electron beamdeposition, cathodic arc deposition, low pressure chemical vapordeposition and wet chemistry techniques such as layer by layerdeposition, sol-gel deposition, or Langmuir blodgett. Alternatively orin addition, the primer layer can be applied by spray coating, dipcoating, brushing, spin coating, doctor blade coating, and the like.

The primer layer can have a percent transmittance of about 40% or less,about 30% or less, about 20% or less, about 15% or less, about 10% orless, about 5% or less, or about 1% or less, where “less” can includeabout 0% (e.g., 0 to 0.01 or 0 to 0.1), about 1%, about 2.5%, or about5%.

The primer layer can include a paint composition that, upon applying tothe structure, forms a thin layer. The thin layer can be a solid filmhaving a dark color, such as those described above. The paintcomposition can include known paint compositions that can comprise oneor more of the following components: one or more paint resin, one ormore polymers, one or more dyes, and one or more pigments as well aswater, film-forming solvents, drying agents, thickeners, surfactants,anti-skinning agents, plasticizers, mildewcides, mar-resistant agents,anti-flooding agents, and combinations thereof.

The primer layer can comprise a reground, and at least partiallydegraded, polymer layer. The reground, and at least partially degraded,polymer layer can have a dark color, such as those described above.

The primer layer can include a metal layer or the oxide layer. The metallayer or the oxide layer can have a dark color, such as those describedabove. The oxide layer can be a metal oxide, a doped metal oxide, or acombination thereof. The metal layer, the metal oxide or the doped metaloxide can include the following: the transition metals, the metalloids,the lanthanides, and the actinides, as well as nitrides, oxynitrides,sulfides, sulfates, selenides, tellurides and a combination of these.The metal oxide can include titanium oxide, aluminum oxide, silicondioxide, tin dioxide, chromia, iron oxide, nickel oxide, silver oxide,cobalt oxide, zinc oxide, platinum oxide, palladium oxide, vanadiumoxide, molybdenum oxide, lead oxide, and combinations thereof as well asdoped versions of each. In some aspects, the primer layer can consistessentially of a metal oxide. In some aspects, the primer layer canconsist essentially of titanium dioxide or silicon dioxide. In someaspects, the primer layer can consist essentially of titanium dioxide.The metal oxide can be doped with water, inert gasses (e.g., argon),reactive gasses (e.g., oxygen or nitrogen), metals, small molecules, anda combination thereof. In some aspects, the primer layer can consistessentially of a doped metal oxide or a doped metal oxynitride or both.

The primer layer can be a coating on the surface of the article. Thecoating can be chemically bonded (e.g., covalently bonded, ionicallybonded, hydrogen bonded, and the like) to the surface of the article.The coating has been found to bond well to a surface made of a polymericmaterial. In an example, the surface of the article can be made of apolymeric material such as a polyurethane, including a thermoplasticpolyurethane (TPU), as those described herein.

The coating can be a crosslinked coating that includes one or morecolorants such as solid pigment particles or dye. The crosslinkedcoating can be a matrix of crosslinked polymers (e.g., a crosslinkedpolyester polyurethane polymer or copolymer). The colorants can beentrapped in the coating, including entrapped in the matrix ofcrosslinked polymers. The solid pigment particles or dye can bephysically entrapped in the crosslinked polymer matrix, can bechemically bonded (e.g., covalently bonded, ionically bonded, hydrogenbonded, and the like, with the coating including the polymeric matrix orwith the material forming the surface of the article to which thecoating is applied), or a combination of physically bonded andchemically bonded with the coating or article. The crosslinked coatingcan have a thickness of about 0.01 micrometers to 1000 micrometers.

The coating can be a product (or also referred to as “crosslinkedproduct”) of crosslinking a polymeric coating composition. The polymericcoating composition can include one or more colorants (e.g., solidpigment particles or dye) in a dispersion of polymers. The dispersion ofpolymers can include a water-borne dispersion of polymers such as awater-borne dispersion of polyurethane polymers, including polyesterpolyurethane copolymers). The water-borne dispersion of polymers can becrosslinked to entrap the colorants. The colorants can be physicallyentrapped in the crosslinked product, can be chemically bonded (e.g.,covalently bonded, ionically bonded, hydrogen bonded, and the like, withthe crosslinked copolymer matrix), or can be both physically bonded andchemically bonded with the crosslinked product. The product can beformed by crosslinking the polymeric coating composition. The productcan have a thickness of about 0.01 micrometer to 1000 micrometers.

The coating can include colorants such a pigment (e.g., a solid pigmentparticle) or a dye. The solid pigment particles can include inorganicpigments such as metal and metal oxides such as homogeneous inorganicpigments, core-shell pigments and the like, as well as carbon pigments(e.g., carbon black), clay earth pigments, and ultramarine pigments. Thesolid pigment particles can be biological or organic pigments. The solidpigment particles can be of a type known in the art as an extenderpigment, which include, but are not limited to, calcium carbonate,calcium silicate, mica, clay, silica, barium sulfate and the like. Theamount of the solid pigment particles sufficient to achieve the desiredcolor intensity, shade, and opacity, can be in amounts up to about 5percent to 25 percent or more by weight of the coating. The pigments caninclude those sold by KP Pigments such as pearl pigments, color shiftpigments (e.g., CALYPSO, JEDI, VERO, BLACKHOLE, LYNX, ROSE GOLD, and thelike), hypershift pigments, interference pigments and the like.

The colorant can be a dye such as an anionic dye, a cationic dye, adirect dye, a metal complex dye, a basic dye, a disperse dye, a solventdye, a polymeric dye, a polymeric dye colorant, or a nonionic dye, wherethe coating can include one or more dyes and/or types of dyes. The dyecan be a water-miscible dye. The dye can be a solubilized dye. Theanionic dye can be an acid dye. The dye can be applied separately fromthe coating (e.g., either before or after the coating is applied and/orcured).

Acid dyes are water-soluble anionic dyes. Acid dyes are available in awide variety, from dull tones to brilliant shades. Chemically, acid dyesinclude azo, anthraquinone and triarylmethane compounds. The “ColorIndex” (C.I.), published jointly by the Society of Dyers and Colourists(UK) and by the American Association of Textile Chemists and Colorists(USA), is the most extensive compendium of dyes and pigments for largescale coloration purposes, including 12000 products under 2000 C.I.generic names. In the C.I. each compound is presented with two numbersreferring to the coloristic and chemical classification. The “genericname” refers to the field of application and/or method of coloration,while the other number is the “constitution number.” Examples of aciddyes include Acid Yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110,116, 127, 151, 158:1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246,and 250; Acid Red, 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183,184, 186, 194, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278,283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419,and 447; Acid Violet 3, 5, 7, 17, 54, 90, and 92; Acid Brown 4, 14, 15,45, 50, 58, 75, 97, 98, 147, 160:1, 161, 165, 191, 235, 239, 248, 282,283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414,420, 422, 425, 432, and 434; Acid Orange 3, 7, 10, 19, 33, 56, 60, 61,67, 74, 80, 86, 94, 139, 142, 144, 154, and 162; Acid Blue 1, 7, 9, 15,92, 133, 158, 185, 193, 277, 277:1, 314, 324, 335, and 342; Acid Green1, 12, 68:1, 73, 80, 104, 114, and 119; Acid Black 1, 26, 52, 58, 60,64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, 235, andcombinations of these. The acid dyes may be used singly or in anycombination in the ink composition.

Acid dyes and nonionic disperse dyes are commercially available frommany sources, including Dystar L.P., Charlotte, NC under the tradenameTELON, Huntsman Corporation, Woodlands, TX, USA under the tradenameERIONYL and TECTILON, BASF SE, Ludwigshafen, Germany under the tradenameBASACID, and Bezema AG, Montlingen, Switzerland under the tradenameBemacid.

The colorant can include the dye and a quaternary (tetraalkyl) ammoniumsalt, in particular when the dye is acidic dye. The quaternary(tetraalkyl) ammonium salt can react with the dye (e.g., acid dye) toform a complexed dye that can be used in the coating. The “alkyl” groupcan include C1 to C10 alkyl groups. The quaternary (tetraalkyl) ammoniumsalt can be selected from soluble tetrabutylammonium compounds andtetrahexylammonium compounds. The counterion of the quaternary ammoniumsalt should be selected so that the quaternary ammonium salt forms astable solution with the dye (e.g., anionic dye). The quaternaryammonium compound may be, for example, a halide (such as chloride,bromide or iodide), hydroxide, sulfate, sulfite, carbonate, perchlorate,chlorate, bromate, iodate, nitrate, nitrite, phosphate, phosphite,hexfluorophosphite, borate, tetrafluoroborate, cyanide, isocyanide,azide, thiosulfate, thiocyanate, or carboxylate (such as acetate oroxalate). The tetraalkylammonium compound can be or include atetrabutylammonium halide or tetrahexylammonium halide, particularly atetrabutylammonium bromide or chloride or a tetrahexylammonium bromideor chloride. The coating (e.g., coating, polymeric coating composition(prior to curing) can include about 1 to 15 weight percent of thequaternary ammonium salt. The molar ratio of the acid dye to thequaternary ammonium compound can range from about 3:1 to 1:3 or about1.5:1 to 1:1.5.

The coating (e.g., coating, polymeric coating composition (prior tocuring), monomers and/or polymers of the matrix of crosslinked polymers,or precursors of the coating) can include a cross-linker, whichfunctions to crosslink the polymeric components of the coating. Thecross-linker can bea water-borne cross-linker. The cross-linker caninclude one or more of the following: a polycarboxylic acid crosslinkingagent, an aldehyde crosslinking agent, a polyisocyanate crosslinkingagent, or a combination thereof. The polycarboxylic acid crosslinkingagent can be a polycarboxylic acid having from 2 to 9 carbon atoms. Forexample, the cross-linker can include a polyacrylic acid, a polymaleicacid, a copolymer of acid, a copolymer of maleic acid, fumaric acid, or1, 2, 3, 4-butanetetracarboxylic acid. The concentration of thecross-linker can be about 0.01 to 5 weight percent or 1 to 3 weightpercent of the coating.

The coating (e.g., coating, polymeric coating composition (prior tocuring), monomers and/or polymers of the matrix of crosslinked polymers,or precursors of the coating) can include a solvent. The solvent can bean organic solvent. The organic solvent can be a water-miscible organicsolvent. The coating may not include water, or may be essentially freeof water. For example, the solvent can be or includes acetone, ethanol,2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethylketone, 1-butanol, t-butanol, or any mixture thereof.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe article, components of the article, structures, layers, films,bladders, foams, primer layer, coating, and like the. The polymer can bea thermoset polymer or a thermoplastic polymer. The polymer can be anelastomeric polymer, including an elastomeric thermoset polymer or anelastomeric thermoplastic polymer. The polymer can be selected from:polyurethanes (including elastomeric polyurethanes, thermoplasticpolyurethanes (TPUs), and elastomeric TPUs), polyesters, polyethers,polyamides, vinyl polymers (e.g., copolymers of vinyl alcohol, vinylesters, ethylene, acrylates, methacrylates, styrene, and so on),polyacrylonitriles, polyphenylene ethers, polycarbonates, polyureas,polystyrenes, co-polymers thereof (including polyester-polyurethanes,polyether-polyurethanes, polycarbonate-polyurethanes, polyether blockpolyamides (PEBAs), and styrene block copolymers), and any combinationthereof, as described herein. The polymer can include one or morepolymers selected from the group consisting of polyesters, polyethers,polyamides, polyurethanes, polyolefins copolymers of each, andcombinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

As previously described, the polymer can be a thermoplastic polymer. Ingeneral, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm³/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm³/10 min to about 28 cm³/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

The polymer can be a thermoset polymer. As used herein, a “thermosetpolymer” is understood to refer to a polymer which cannot be heated andmelted, as its melting temperature is at or above its decompositiontemperature. A “thermoset material” refers to a material which comprisesat least one thermoset polymer. The thermoset polymer and/or thermosetmaterial can be prepared from a precursor (e.g., an uncured or partiallycured polymer or material) using thermal energy and/or actinic radiation(e.g., ultraviolet radiation, visible radiation, high energy radiation,infrared radiation) to form a partially cured or fully cured polymer ormaterial which no longer remains fully thermoplastic. In some cases, thecured or partially cured polymer or material may remain thermoelasticproperties, in that it is possible to partially soften and mold thepolymer or material at elevated temperatures and/or pressures, but it isnot possible to melt the polymer or material. The curing can bepromoted, for example, with the use of high pressure and/or a catalyst.In many examples, the curing process is irreversible since it results incross-linking and/or polymerization reactions of the precursors. Theuncured or partially cured polymers or materials can be malleable orliquid prior to curing. In some cases, the uncured or partially curedpolymers or materials can be molded into their final shape, or used asadhesives. Once hardened, a thermoset polymer or material cannot bere-melted in order to be reshaped. The textured surface can be formed bypartially or fully curing an uncured precursor material to lock in thetextured surface.

Polyurethane

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Alternatively, the polymer can be athermoset polyurethane. Additionally, polyurethane can be an elastomericpolyurethane, including an elastomeric TPU or an elastomeric thermosetpolyurethane. The elastomeric polyurethane can include hard and softsegments. The hard segments can comprise or consist of urethane segments(e.g., isocyanate-derived segments). The soft segments can comprise orconsist of alkoxy segments (e.g., polyol-derived segments includingpolyether segments, or polyester segments, or a combination of polyethersegments and polyester segments). The polyurethane can comprise orconsist essentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R₁ group and R₂ group independently is an aliphatic or aromaticgroup. Optionally, each R₂ can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R₃ includes the chain extender.As with each R₁ and R₂, each R₃ independently is an aliphatic oraromatic functional group.

Each R₁ group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R₁ group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R₁ groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R₁group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term C_(n) itmeans the alkene or alkylene group has “n” carbon atoms. For example,C₁₋₆ alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5,or 6 carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MD1), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R₁ group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4-′dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. Thepolymer chains can be substantially free of aromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H₁₂ aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H₁₂aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R₃ group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R₂ group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R₂ group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R₂ group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term C_(n) it means the alkyl group has “n” carbonatoms. For example, C₄ alkyl refers to an alkyl group that has 4 carbonatoms. C₁₋₇ alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R₂ group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol, 1,5,diethyleneglycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R₂ group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol, 1,5-diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkenylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkenylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R₂ group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R₂ is an aliphatic or aromatic group having pendant amino,carboxylate, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R₂ group in the polyurethane can include apolytetramethylene oxide group. At least one R₂ group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in E.P. Patent No. 2 462 908, which is herebyincorporated by reference. For example, the R₂ group can be derived fromthe reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

At least one R₂ of the polyurethane can be a polysiloxane, In thesecases, the R₂ group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R₅ independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R₄ group can independently be a H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R₄ group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R₅ group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R₅ group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R₅ group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). The crosslinked polyurethanecan be a thermoset polymer. This crosslinked polymeric network can beproduced by polymerizing one or more isocyanates with one or morepolyamino compounds, polysulfhydryl compounds, or combinations thereof,as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R₁ group in Formula 1, and the R₁ and R₃ groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R₂ group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

The polyurethane can be a thermoplastic polyurethane composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, IL, USA), “PELLETHANE” 2355-85ATP and 2355-95AE(Dow Chemical Company of Midland, MI, USA.), “ESTANE” (e.g., ALR G 500,or 58213; Lubrizol, Countryside, IL, USA).

One or more of the polyurethanes (e.g., those used in the primer as thecoating (e.g., water-dispersible polyurethane)) can be produced bypolymerizing one or more isocyanates with one or more polyols to producecopolymer chains having carbamate linkages (—N(C═O)O—) and one or morewater-dispersible enhancing moieties, where the polymer chain includesone or more water-dispersible enhancing moieties (e.g., a monomer inpolymer chain). The water-dispersible polyurethane can also be referredto as “a water-borne polyurethane polymer dispersion.” Thewater-dispersible enhancing moiety can be added to the chain of Formula1 or 2 (e.g., within the chain and/or onto the chain as a side chain).Inclusion of the water-dispersible enhancing moiety enables theformation of a water-borne polyurethane dispersion. The term“water-borne” herein means the continuous phase of the dispersion orformulation of about 50 weight percent to 100 weight percent water,about 60 weight percent to 100 weight percent water, about 70 weightpercent to 100 weight percent water, or about 100 weight percent water.The term “water-borne dispersion” refers to a dispersion of a component(e.g., polymer, cross-linker, and the like) in water withoutco-solvents. The co-solvent can be used in the water-borne dispersionand the co-solvent can be an organic solvent. Additional detailregarding the polymers, polyurethanes, isocyantes and the polyols areprovided below.

The polyurethane (e.g., a water-borne polyurethane polymer dispersion)can include one or more water-dispersible enhancing moieties. Thewater-dispersible enhancing moiety can have at least one hydrophilic(e.g., poly(ethylene oxide)), ionic or potentially ionic group to assistdispersion of the polyurethane, thereby enhancing the stability of thedispersions. A water-dispersible polyurethane can be formed byincorporating a moiety bearing at least one hydrophilic group or a groupthat can be made hydrophilic (e.g., by chemical modifications such asneutralization) into the polymer chain. For example, these compounds canbe nonionic, anionic, cationic or zwitterionic or the combinationthereof. In one example, anionic groups such as carboxylic acid groupscan be incorporated into the chain in an inactive form and subsequentlyactivated by a salt-forming compound, such as a tertiary amine. Otherwater-dispersible enhancing moieties can also be reacted into thebackbone through urethane linkages or urea linkages, including lateralor terminal hydrophilic ethylene oxide or ureido units.

The water-dispersible enhancing moiety can be a one that includescarboxyl groups. Water-dispersible enhancing moiety that include acarboxyl group can be formed from hydroxy-carboxylic acids having thegeneral formula (HO)_(x)Q(COOH)_(y), where Q can be a straight orbranched bivalent hydrocarbon radical containing 1 to 12 carbon atoms,and x and y can each independently be 1 to 3. Illustrative examplesinclude dimethylolpropanoic acid (DMPA), dimethylol butanoic acid(DMBA), citric acid, tartaric acid, glycolic acid, lactic acid, malicacid, dihydroxymalic acid, dihydroxytartaric acid, and the like, andmixtures thereof.

The water-dispersible enhancing moiety can include reactive polymericpolyol components that contain pendant anionic groups that can bepolymerized into the backbone to impart water dispersiblecharacteristics to the polyurethane. Anionic functional polymericpolyols can include anionic polyester polyols, anionic polyetherpolyols, and anionic polycarbonate polyols, where additional detail isprovided in U.S. Pat. No. 5,334,690.

The water-dispersible enhancing moiety can include a side chainhydrophilic monomer. For example, the water-dispersible enhancing moietyincluding the side chain hydrophilic monomer can include alkylene oxidepolymers and copolymers in which the alkylene oxide groups have from2-10 carbon atoms as shown in U.S. Pat. No. 6,897,281. Additional typesof water-dispersible enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide,or a thermoset polyamide. The polyamide can be an elastomeric polyamide,including an elastomeric thermoplastic polyamide or an elastomericthermoset polyamide. The polyamide can be a polyamide homopolymer havingrepeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R₆ group represents the portion of thepolyamide derived from the lactam or amino acid.

The R₆ group can be derived from a lactam. The R₆ group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R₆ group can be derived from caprolactam orlaurolactam. The R₆ group can be derived from one or more amino acids.The R₆ group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R₆ groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R₇ group represents the portion of thepolyamide derived from the diamino compound, and the R₈ group representsthe portion derived from the dicarboxylic acid compound:

The R₇ group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R₇ group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD),m-xylylene diamine (MXD), and1,5-pentamine diamine. The R₈ group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR₈ can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R₈ can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an α, ω-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH₂)₁₀—COOH can be used; and a lactam such as caprolactam andlauryllactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine that can be an aliphatic diaminecontaining from 6 to 12 atoms and can be acyclic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM).

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 Pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)₄, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies. In other cases, the crosslinked polyamide is a thermosetpolymer.

Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester, or a thermoset polyester. Additionally, thepolyester can be an elastomeric polyester, including a thermoplasticpolyester or a thermoset elastomeric polyester. The polyester can beformed by reaction of one or more carboxylic acids, or its ester-formingderivatives, with one or more bivalent or multivalent aliphatic,alicyclic, aromatic or araliphatic alcohols or a bisphenol. Thepolyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycondensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1,3-propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(α-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin or a thermoset polyolefin.Additionally, the polyolefin can be an elastomeric polyolefin, includinga thermoplastic elastomeric polyolefin or a thermoset elastomericpolyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g., metallocene-catalyzed blockcopolymers of ethylene and α-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, a ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, Vlb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, Vlb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic and/or thermosetting material can further comprise oneor more processing aids. The processing aid can be a non-polymericmaterial. These processing aids can be independently selected from thegroup including, but not limited to, curing agents, initiators,plasticizers, mold release agents, lubricants, antioxidants, flameretardants, dyes, pigments, reinforcing and non-reinforcing fillers,fiber reinforcements, and light stabilizers.

The component can include one or more bladders and the bladder caninclude the structural color structure. The bladder can be unfilled,partially inflated, or fully inflated when the structural design (e.g.,optical element) is adhered to the bladder. The bladder is a bladdercapable of including a volume of a fluid. An unfilled bladder is afluid-fillable bladder and a filled bladder has been at least partiallyinflated with a fluid at a pressure equal to or greater than atmosphericpressure. When disposed onto or incorporated into an article, thebladder is generally, at that point, a fluid-filled bladder. The fluidbe a gas or a liquid. The gas can include air, nitrogen gas (N₂), orother appropriate gas.

The bladder can have a gas transmission rate for nitrogen gas, forexample, where a bladder wall of a given thickness has a gastransmission rate for nitrogen that is at least about ten times lowerthan the gas transmission rate for nitrogen of a butyl rubber layer ofsubstantially the same thickness as the thickness of the bladderdescribed herein. The bladder can have a first bladder wall having afirst bladder wall thickness (e.g., about 0.1 to 40 mils). The bladdercan have a first bladder wall that can have a gas transmission rate(GTR) for nitrogen gas of less than about 15 cm³/m²·atm·day, less thanabout 10 m³/m²·atm·day, less than about 5 cm³/m²·atm·day, less thanabout 1 cm³/m²·atm·day (e.g., from about 0.001 cm³/m²·atm·day to about 1cm³/m²·atm·day, about 0.01 cm³/m²·atm·day to about 1 cm³/m²·atm·day orabout 0.1 cm³/m²·atm·day to about 1 cm³/m²·atm·day) for an average wallthickness of 20 mils. The bladder can have a first bladder wall having afirst bladder wall thickness, where the first bladder wall has a gastransmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage wall thickness of 20 mils.

In an aspect, the bladder has a bladder wall having an interior-facingside and an exterior (or externally)-facing side, where the interior (orinternally)-facing side defines at least a portion of an interior regionof the bladder. The multi-layer optical film (or optical element) havinga first side and a second opposing side can be disposed on theexterior-facing side of the bladder, the interior-facing side of thebladder, or both. The exterior-facing side of the bladder, theinterior-facing side of the bladder, or both can include a plurality oftopographical structures (or profile features) extending from theexterior-facing side of the bladder wall, the interior-facing side ofthe bladder, or both, where the first side or the second side of themulti-layer optical film is disposed on the exterior-facing side of thebladder wall and covering the plurality of topographical structures, theinterior-facing side of the bladder wall and covering the plurality oftopographical structures, or both, and wherein the multi-layer opticalfilm imparts a structural color to the bladder wall. The primer layercan be disposed on the exterior-facing side of the bladder, theinterior-facing side of the bladder, or both, between the bladder walland the multi-layer optical film.

In a particular aspect, the bladder can include a top wall operablysecured to the footwear upper, a bottom wall opposite the top wall, andone or more sidewalls extending between the top wall and the bottom wallof the inflated bladder. The top wall, the bottom wall, and the one ormore sidewalls collectively define an interior region of the inflatedbladder, and wherein the one or more sidewalls each comprise anexterior-facing side. The multi-layer optical film having a first sideand a second opposing side can be disposed on the exterior-facing sideof the bladder, the interior-facing side of the bladder, or both. Theexterior-facing side of the bladder, the interior-facing side of thebladder, or both can include a plurality of topographical structuresextending from the exterior-facing side of the bladder wall, theinterior-facing side of the bladder, or both, where the first side orthe second side of the multi-layer optical film is disposed on theexterior-facing side of the bladder wall and covering the plurality oftopographical structures, the interior-facing side of the bladder walland covering the plurality of topographical structures, or both, andwherein the multi-layer optical film imparts a structural color to thebladder wall. The primer layer can be disposed on the exterior-facingside of the bladder, the interior-facing side of the bladder, or both,between the bladder wall and the multi-layer optical film.

An accepted method for measuring the relative permeance, permeability,and diffusion of inflated bladders is ASTM D-1434-82-V. See, e.g., U.S.Pat. No. 6,127,026, which is incorporated by reference as if fully setforth herein. According to ASTM D-1434-82-V, permeance, permeability anddiffusion are measured by the following formulae:

Permeance

(quantity of gas)/[(area)×(time)×(pressuredifference)]=permeance(GTR)/(pressure difference)=cm³/m²·atm·day (i.e.,24 hours)

Permeability

[(quantity of gas)×(film thickness)][(area)×(time)×(pressuredifference)]=permeability [(GTR)×(film thickness)]/(pressuredifference)=[(cm³)(mil)]/m²·atm·day(i.e., 24 hours)

Diffusion at one atmosphere

(quantity of gas)/[(area)×(time)]=GTR=cm³/m²·day(i.e., 24 hours)

The bladder can include a bladder wall that includes a film including atleast one polymeric layer or at least two or more polymeric layers. Eachof the polymeric layers can be about 0.1 to 40 mils in thickness.

The polymeric layer can be formed of polymer material such as athermoplastic material. The thermoplastic material can include anelastomeric material, such as a thermoplastic elastomeric material. Thethermoplastic materials can include thermoplastic polyurethane (TPU),such as those described herein. The thermoplastic materials can includepolyester-based TPU, polyether-based TPU, polycaprolactone-based TPU,polycarbonate-based TPU, polysiloxane-based TPU, or combinationsthereof. Non-limiting examples of thermoplastic material that can beused include: “PELLETHANE” 2355-85ATP and 2355-95AE (Dow ChemicalCompany of Midland, MI., USA), “ELASTOLLAN” (BASF Corporation,Wyandotte, MI, USA) and “ESTANE” (Lubrizol, Brecksville, OH, USA), allof which are either ester or ether based. Additional thermoplasticmaterial can include those described in U.S. Pat. Nos. 5,713,141;5,952,065; 6,082,025; 6,127,026; 6,013,340; 6,203,868; and 6,321,465,which are incorporated herein by reference.

The polymeric layer can be formed of one or more of the following:ethylene-vinyl alcohol copolymers (EVOH), poly(vinyl chloride),polyvinylidene polymers and copolymers (e.g., polyvinylidene chloride),polyamides (e.g., amorphous polyamides), acrylonitrile polymers (e.g.,acrylonitrile-methyl acrylate copolymers), polyurethane engineeringplastics, polymethylpentene resins, ethylene-carbon monoxide copolymers,liquid crystal polymers, polyethylene terephthalate, polyether imides,polyacrylic imides, and other polymeric materials known to haverelatively low gas transmission rates. Blends and alloys of thesematerials as well as with the TPUs described herein and optionallyincluding combinations of polyimides and crystalline polymers, are alsosuitable. For instance, blends of polyimides and liquid crystalpolymers, blends of polyamides and polyethylene terephthalate, andblends of polyamides with styrenics are suitable.

Specific examples of polymeric materials of the polymeric layer caninclude acrylonitrile copolymers such as “BAREX” resins, available fromIneos (Rolle, Switzerland); polyurethane engineering plastics such as“ISPLAST” ETPU available from Lubrizol (Brecksville, OH, USA);ethylene-vinyl alcohol copolymers marketed under the tradenames “EVAL”by Kuraray (Houston, TX, USA), “SOARNOL” by Nippon Gohsei (Hull,England), and “SELAR OH” by DuPont (Wilmington, DE, USA);polyvinylidiene chloride available from S.C. Johnson (Racine, WI, USA)under the tradename “SARAN”, and from Solvay (Brussels, Belgium) underthe tradename “IXAN”; liquid crystal polymers such as “VECTRA” fromCelanese (Irving, TX, USA) and “XYDAR” from Solvay; “MDX6” nylon, andamorphous nylons such as “NOVAMID” X21 from Koninklijke DSM N.V(Heerlen, Netherlands), “SELAR PA” from DuPont; polyetherimides soldunder the tradename “ULTEM” by SABIC (Riyadh, Saudi Arabia); poly(vinylalcohol)s; and polymethylpentene resins available from Mitsui Chemicals(Tokyo, Japan) under the tradename “TPX”.

Each polymeric layer of the film can be formed of a thermoplasticmaterial which can include a combination of thermoplastic polymers. Inaddition to one or more thermoplastic polymers, the thermoplasticmaterial can optionally include a colorant, a filler, a processing aid,a free radical scavenger, an ultraviolet light absorber, and the like.Each polymeric layer of the film can be made of a different ofthermoplastic material including a different type of thermoplasticpolymer.

The bladder can be made by applying heat, pressure and/or vacuum to afilm. The bladder (e.g., one or more polymeric layers) can be formedusing one or more polymeric materials, and forming the bladder using oneor more processing techniques including, for example, extrusion, blowmolding, injection molding, vacuum molding, rotary molding, transfermolding, pressure forming, heat sealing, casting, low-pressure casting,spin casting, reaction injection molding, radio frequency (RF) welding,and the like. The bladder can be made by co-extrusion followed by heatsealing or welding to give an inflatable bladder, which can optionallyinclude one or more valves (e.g., one way valves) that allows thebladder to be filled with the fluid (e.g., gas).

In examples where the bladder includes the structural color structure,the optical element can be disposed onto the internally-facing surface(side) of the bladder or the externally-facing surface (side) of thebladder. The textured layer can be the internally-facing surface (side)or the externally-facing surface (side) of the bladder. The relativeconstruction can include: optical element/internally-facing surface ofthe bladder///externally-facing surface of the bladder orinternally-facing surface of the bladder///externally-facing surface ofthe bladder/optical element. The optical element can include the opticallayer and optionally the primer layer and texture structure. Thetextured layer can be the internally-facing surface (side) or theexternally-facing surface (side) of the bladder (e.g., where theinternally-facing or externally-facing side is made of a thermoplasticmaterial) and the primer layer disposed thereon and the optical elementdisposed on the primer layer.

In articles of footwear that include a textile, the optical element canbe disposed onto the textile. The textile or at least an outer layer ofthe textile can includes a thermoplastic material that the opticalelement can disposed onto. The textile can be a nonwoven textile, asynthetic leather, a knit textile, or a woven textile. The textile cancomprise a first fiber or a first yarn, where the first fiber or thefirst yarn can include at least an outer layer formed of the firstthermoplastic material. A region of the first or second side of thestructure onto which the optical element is disposed can include thefirst fiber or the first yarn in a non-filamentous conformation. Theoptical element can be disposed onto the textile or the textile can beprocessed so that the optical element can be disposed onto the textile.The textured surface can be made of or formed from the textile surface.The primer layer can be disposed on the textile surface and then theoptical element can be disposed onto the primer layer. The textilesurface can be used to form the textured surface, and either before orafter this, the primer layer can be optionally applied to the texturedsurface prior to disposing the optical element to the textile.

A “textile” may be defined as any material manufactured from fibers,filaments, or yarns characterized by flexibility, fineness, and a highratio of length to thickness. Textiles generally fall into twocategories. The first category includes textiles produced directly fromwebs of filaments or fibers by randomly interlocking to constructnon-woven fabrics and felts. The second category includes textilesformed through a mechanical manipulation of yarn, thereby producing awoven fabric, a knitted fabric, a braided fabric, a crocheted fabric,and the like.

The terms “filament,” “fiber,” or “fibers” as used herein refer tomaterials that are in the form of discrete elongated pieces that aresignificantly longer than they are wide. The fiber can include natural,manmade or synthetic fibers. The fibers may be produced by conventionaltechniques, such as extrusion, electrospinning, interfacialpolymerization, pulling, and the like. The fibers can include carbonfibers, boron fibers, silicon carbide fibers, titania fibers, aluminafibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, andNE glasses and quartz, or the like. The fibers can be fibers formed fromsynthetic polymers capable of forming fibers such as poly(ether ketone),polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters,polyolefins (e.g., polyethylene, polypropylene), aromatic polyamides(e.g., an aramid polymer such as para-aramid fibers and meta-aramidfibers), aromatic polyimides, polybenzimidazoles, polyetherimides,polytetrafluoroethylene, acrylic, modacrylic, poly(vinyl alcohol),polyamides, polyurethanes, and copolymers such as polyether-polyureacopolymers, polyester-polyurethanes, polyether block amide copolymers,or the like. The fibers can be natural fibers (e.g., silk, wool,cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fibers can beman-made fibers from regenerated natural polymers, such as rayon,lyocell, acetate, triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made andsynthetic fibers are generally extruded in substantially continuousstrands. Alternatively, the fibers can be staple fibers, such as, forexample, cotton fibers or extruded synthetic polymer fibers can be cutto form staple fibers of relatively uniform length. The staple fiber canhave a have a length of about 1 millimeter to 100 centimeters or more aswell as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Naturalfibers can have a natural cross-section, or can have a modifiedcross-sectional shape (e.g., with processes such as mercerization).Man-made or synthetic fibers can be extruded to provide a strand havinga predetermined cross-sectional shape. The cross-sectional shape of afiber can affect its properties, such as its softness, luster, andwicking ability. The fibers can have round or essentially round crosssections. Alternatively, the fibers can have non-round cross sections,such as flat, oval, octagonal, rectangular, wedge-shaped, triangular,dog-bone, multi-lobal, multi-channel, hollow, core-shell, or othershapes.

The fiber can be processed. For example, the properties of fibers can beaffected, at least in part, by processes such as drawing (stretching)the fibers, annealing (hardening) the fibers, and/or crimping ortexturizing the fibers.

In some cases a fiber can be a multi-component fiber, such as onecomprising two or more co-extruded polymeric materials. The two or moreco-extruded polymeric materials can be extruded in a core-sheath,islands-in-the-sea, segmented-pie, striped, or side-by-sideconfiguration. A multi-component fiber can be processed in order to forma plurality of smaller fibers (e.g., microfibers) from a single fiber,for example, by remove a sacrificial material.

The fiber can be a carbon fiber such as TARIFYL produced by FormosaPlastics Corp. of Kaohsiung City, Taiwan, (e.g., 12,000, 24,000, and48,000 fiber tows, specifically fiber types TC-35 and TC-35R), carbonfiber produced by SGL Group of Wiesbaden, Germany (e.g., 50,000 fibertow), carbon fiber produced by Hyosung of Seoul, South Korea, carbonfiber produced by Toho Tenax of Tokyo, Japan, fiberglass produced byJushi Group Co., LTD of Zhejiang, China (e.g., E6, 318, silane-basedsizing, filament diameters 14, 15, 17, 21, and 24 micrometers), andpolyester fibers produced by Amann Group of Bonningheim, Germany (e.g.,SERAFILE 200/2 non-lubricated polyester filament and SERAFILE COMPHIL200/2 lubricated polyester filament).

A plurality of fibers includes 2 to hundreds or thousands or morefibers. The plurality of fibers can be in the form of bundles of strandsof fibers, referred to as tows, or in the form of relatively alignedstaple fibers referred to as sliver and roving. A single type fiber canbe used either alone or in combination with one or more different typesof fibers by co-mingling two or more types of fibers. Examples ofco-mingled fibers include polyester fibers with cotton fibers, glassfibers with carbon fibers, carbon fibers with aromatic polyimide(aramid) fibers, and aromatic polyimide fibers with glass fibers.

As used herein, the term “yarn” refers to an assembly formed of one ormore fibers, wherein the strand has a substantial length and arelatively small cross-section, and is suitable for use in theproduction of textiles by hand or by machine, including textiles madeusing weaving, knitting, crocheting, braiding, sewing, embroidery, orropemaking techniques. Thread is a type of yarn commonly used forsewing.

Yarns can be made using fibers formed of natural, man-made and syntheticmaterials. Synthetic fibers are most commonly used to make spun yarnsfrom staple fibers, and filament yarns. Spun yarn is made by arrangingand twisting staple fibers together to make a cohesive strand. Theprocess of forming a yarn from staple fibers typically includes cardingand drawing the fibers to form sliver, drawing out and twisting thesliver to form roving, and spinning the roving to form a strand.Multiple strands can be plied (twisted together) to make a thicker yarn.The twist direction of the staple fibers and of the plies can affect thefinal properties of the yarn. A filament yarn can be formed of a singlelong, substantially continuous filament, which is conventionallyreferred to as a “monofilament yarn,” or a plurality of individualfilaments grouped together. A filament yarn can also be formed of two ormore long, substantially continuous filaments which are grouped togetherby grouping the filaments together by twisting them or entangling themor both. As with staple yarns, multiple strands can be plied together toform a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing,thermal or mechanical treating, or coating with a material such as asynthetic polymer. The fibers, yarns, or textiles, or any combinationthereof, used in the disclosed articles can be sized. Sized fibers,yarns, and/or textiles are coated on at least part of their surface witha sizing composition selected to change the absorption or wearcharacteristics, or for compatibility with other materials. The sizingcomposition facilitates wet-out and wet-through of the coating or resinupon the surface and assists in attaining desired physical properties inthe final article. An exemplary sizing composition can comprise, forexample, epoxy polymers, urethane-modified epoxy polymers, polyesterpolymers, phenol polymers, polyamide polymers, polyurethane polymers,polycarbonate polymers, polyetherimide polymers, polyamideimidepolymers, polystylylpyridine polymers, polyimide polymers bismaleimidepolymers, polysulfone polymers, polyethersulfone polymers,epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarnssuch as single- or double-covered yarns, and corespun yarns.Accordingly, yarns may have a variety of configurations that generallyconform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one ormore of the fibers can be made of thermoplastic material). The yarn canbe made of a thermoplastic material. The yarn can be coated with a layerof a material such as a thermoplastic material.

The linear mass density or weight per unit length of a yarn can beexpressed using various units, including denier (D) and tex. Denier isthe mass in grams of 9000 meters of yarn. The linear mass density of asingle filament of a fiber can also be expressed using denier perfilament (DPF). Tex is the mass in grams of a 1000 meters of yarn.Decitex is another measure of linear mass, and is the mass in grams fora 10,000 meters of yarn.

As used herein, tenacity is understood to refer to the amount of force(expressed in units of weight, for example: pounds, grams, centinewtonsor other units) needed to break a yarn (i.e., the breaking force orbreaking point of the yarn), divided by the linear mass density of theyarn expressed, for example, in (unstrained) denier, decitex, or someother measure of weight per unit length. The breaking force of the yarnis determined by subjecting a sample of the yarn to a known amount offorce, for example, using a strain gauge load cell such as an INSTRONbrand testing system (Norwood, MA, USA). Yarn tenacity and yarn breakingforce are distinct from burst strength or bursting strength of atextile, which is a measure of how much pressure can be applied to thesurface of a textile before the surface bursts.

Generally, in order for a yarn to withstand the forces applied in anindustrial knitting machine, the minimum tenacity required isapproximately 1.5 grams per Denier. Most yarns formed from commoditypolymeric materials generally have tenacities in the range of about 1.5grams per Denier to about 4 grams per Denier. For example, polyesteryarns commonly used in the manufacture of knit uppers for footwear havetenacities in the range of about 2.5 to about 4 grams per Denier. Yarnsformed from commodity polymeric materials which are considered to havehigh tenacities generally have tenacities in the range of about 5 gramsper Denier to about 10 grams per Denier. For example, commerciallyavailable package dyed polyethylene terephthalate yarn from NationalSpinning (Washington, NC, USA) has a tenacity of about 6 grams perDenier, and commercially available solution dyed polyethyleneterephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has atenacity of about 7 grams per Denier. Yarns formed from high performancepolymeric materials generally have tenacities of about 11 grams perDenier or greater. For example, yarns formed of aramid fiber typicallyhave tenacities of about 20 grams per Denier, and yarns formed ofultra-high molecular weight polyethylene (UHMWPE) having tenacitiesgreater than 30 grams per Denier are available from Dyneema (Stanley,NC, USA) and Spectra (Honeywell-Spectra, Colonial Heights, VA, USA).

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The yarns utilized in interweaving are conventionallyreferred to as “warp” and “weft.” A woven textile includes include awarp yarn and a weft yarn. The warp yarn extends in a first direction,and the weft strand extends in a second direction that is substantiallyperpendicular to the first direction. Intertwining and twistingencompasses various procedures, such as braiding and knotting, whereyarns intertwine with each other to form a textile. Interloopinginvolves the formation of a plurality of columns of intermeshed loops,with knitting being the most common method of interlooping. The textilemay be primarily formed from one or more yarns that aremechanically-manipulated, for example, through interweaving,intertwining and twisting, and/or interlooping processes, as mentionedabove.

The textile can be a nonwoven textile. Generally, a nonwoven textile orfabric is a sheet or web structure made from fibers and/or yarns thatare bonded together. The bond can be a chemical and/or mechanical bond,and can be formed using heat, solvent, adhesive or a combinationthereof. Exemplary nonwoven fabrics are flat or tufted porous sheetsthat are made directly from separate fibers, molten plastic and/orplastic film. They are not made by weaving or knitting and do notnecessarily require converting the fibers to yarn, although yarns can beused as a source of the fibers. Nonwoven textiles are typicallymanufactured by putting small fibers together in the form of a sheet orweb (similar to paper on a paper machine), and then binding them eithermechanically (as in the case of felt, by interlocking them with serratedor barbed needles, or hydro-entanglement such that the inter-fiberfriction results in a stronger fabric), with an adhesive, or thermally(by applying binder (in the form of powder, paste, or polymer melt) andmelting the binder onto the web by increasing temperature). A nonwoventextile can be made from staple fibers (e.g., from wetlaid, airlaid,carding/crosslapping processes), or extruded fibers (e.g., frommeltblown or spunbond processes, or a combination thereof), or acombination thereof. Bonding of the fibers in the nonwoven textile canbe achieved with thermal bonding (with or without calendering),hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting),chemical bonding (e.g., using binders such as latex emulsions orsolution polymers or binder fibers or powders), meltblown bonding (e.g.,fiber is bonded as air attenuated fibers intertangle during simultaneousfiber and web formation).

Now having described embodiments of the disclosure, evaluation ofvarious properties and characteristics described herein are by varioustesting procedures as described herein below.

Method to Determine the Melting Temperature, and Glass TransitionTemperature. The melting temperature and glass transition temperatureare determined using a commercially available Differential Scanningcalorimeter (“DSC”) in accordance with ASTM D3418-97. Briefly, a 10-15gram sample is placed into an aluminum DSC pan and then the lead wassealed with the crimper press. The DSC is configured to scan from −100degrees C. to 225 degrees C. with a 20 degrees C./minute heating rate,hold at 225 degrees C. for 2 minutes, and then cool down to 25 degreesC. at a rate of −10 degrees C./minute. The DSC curve created from thisscan is then analyzed using standard techniques to determine the glasstransition temperature and the melting temperature.

Method to Determine the Melt Flow Index. The melt flow index isdetermined according to the test method detailed in ASTM D1238-13Standard Test Method for Melt Flow Rates of Thermoplastics by ExtrusionPlastometer, using Procedure A described therein. Briefly, the melt flowindex measures the rate of extrusion of thermoplastics through anorifice at a prescribed temperature and load. In the test method,approximately 7 grams of the material is loaded into the barrel of themelt flow apparatus, which has been heated to a temperature specifiedfor the material. A weight specified for the material is applied to aplunger and the molten material is forced through the die. A timedextrudate is collected and weighed. Melt flow rate values are calculatedin grams/10 min.

Various embodiments of the present disclosure are described below ineach of the sets of clauses. In each of the clause sets, “disposing” canbe replaced with “operably disposing.”

Clause Set A

-   -   Clause 1. An article comprising:        -   a component forming at least a portion of the article, the            component having a first surface; and        -   an optical element having a first side and a second side            opposing the first side, wherein the first side of the            optical element, the second side of the optical element, or            both impart a structural color to the component,        -   wherein the first side of the optical element or the second            side of the optical element is disposed on the surface of            the component.    -   Clause 2. The article of any of the proceeding clauses, wherein        at least a portion of the first side of the structure onto which        the first side of the optical element or the second side of the        optical element is disposed includes a first polymeric material.    -   Clause 3. The article of any of the proceeding clauses, wherein        the first side of the structure is an externally-facing side.    -   Clause 4. The article of any of the proceeding clauses, wherein        the article of footwear further comprises a textured surface,        and a combination of the textured surface and the optical        element imparts the structural color.    -   Clause 5. The article of any of the proceeding clauses, wherein        the textured surface is part of a textured structure.    -   Clause 6. The article of any of the proceeding clauses, wherein        the optical element comprises the textured surface.    -   Clause 7. The article of any of the proceeding clauses, wherein        the textured surface is on the first side of the optical        element.    -   Clause 8. The article of any of the proceeding clauses, wherein        the textured surface has a plurality of profile features and        plurality of flat areas.    -   Clause 9. The article of any of the proceeding clauses, wherein        the textured surface includes a plurality of profile features        and flat planar areas, wherein the profile features extend above        the flat areas of the textured surface.    -   Clause 10. The article of any of the proceeding clauses, wherein        the dimensions of the profile features, a shape of the profile        features, a spacing among the plurality of the profile features,        in combination with the optical layer create the structural        color.    -   Clause 11. The article of any of the proceeding clauses, wherein        the profile features are in random positions relative to one        another over an area of the textured surface having a surface        area of at least 5 square millimeters.    -   Clause 12. The article of any of the proceeding clauses, wherein        the spacing among the profile features is set to reduce        distortion effects of the profile features from interfering with        one another in regard to the structural color.    -   Clause 13. The article of any of the proceeding clauses, wherein        the profile features and the flat areas result in at least one        optical layer of the optical element having an undulating        topography, wherein there is a planar region between neighboring        depressions and/or elevations that is planar with the flat        planar areas of the textured surface, wherein the planar region        has dimensions relative to the profile features to impart the        structural color.    -   Clause 14. The article of any of the proceeding clauses, wherein        the optical element includes an optical layer.    -   Clause 15. The article of any of the proceeding clauses, wherein        the optical layer comprises a multilayer reflector or a        multilayer filter.    -   Clause 16. The article of any of the proceeding clauses, wherein        the multilayer reflector has at least two layers, including at        least two adjacent layers having different refractive indices.    -   Clause 17. The article of any of the proceeding clauses, wherein        at least one of the layers of the multilayer reflector has a        thickness that is about one fourth of the wavelength of visible        light to be reflected by the optical element to produce the        structural color.    -   Clause 18. The article of any of the proceeding clauses, wherein        at least one of the layers of the multilayer reflector comprises        a material selected from the group consisting of: silicon        dioxide, titanium dioxide, zinc sulfide, magnesium fluoride,        tantalum pentoxide, and a combination thereof.    -   Clause 19. The article of any of the proceeding clauses, wherein        the optical element, as disposed onto the article, when measured        according to the CIE 1976 color space under a given illumination        condition at three observation angles between −15 degrees and        +60 degrees, has a first color measurement at a first angle of        observation having coordinates L₁* and a₁* and b₁*, and a second        color measurement at a second angle of observation having        coordinates L₂* and a₂* and b_(2*), and a third color        measurement at a third angle of observation having coordinates        L₃* and a₃* and b_(3*), wherein the L₁*, L_(2*), and L₃* values        may be the same or different, wherein the a₁*, a_(2*), and a₃*        coordinate values may be the same or different, wherein the b₁*,        b_(2*), and b₃* coordinate values may be the same or different,        and wherein the range of the combined a₁*, a₂* and a₃* values is        less than about 40% of the overall scale of possible a* values.    -   Clause 20. The article of any of the proceeding clauses, wherein        the range of the combined a₁*, a₂* and a₃* values is less than        about 30% of the overall scale of possible a* values. Clause 21.        The article of any of the proceeding clauses, wherein the range        of the combined a₁*, a₂* and a₃* values is less than about 20%        of the overall scale of possible a* values.    -   Clause 22. The article of any of the proceeding clauses, wherein        the range of the combined a₁*, a₂* and a₃* values is less than        about 10% of the overall scale of possible a* values.    -   Clause 23. The article of any of the proceeding clauses, wherein        the optical element, as disposed onto the article, when measured        according to the CIE 1976 color space under a given illumination        condition at three observation angles between −15 degrees and        +60 degrees, has a first color measurement at a first angle of        observation having coordinates L₁* and a₁* and b₁*, and a second        color measurement at a second angle of observation having        coordinates L₂* and a₂* and b_(2*), and a third color        measurement at a third angle of observation having coordinates        L₃* and a₃* and b_(3*), wherein the L₁*, L_(2*), and L₃* values        may be the same or different, wherein the a₁*, a_(2*), and a₃*        coordinate values may be the same or different, wherein the b₁*,        b_(2*), and b₃* coordinate values may be the same or different,        and wherein the range of the combined b₁*, b₂* and b₃* values is        less than about 40% of the overall scale of possible b* values.    -   Clause 24. The article of any of the proceeding clauses, wherein        the range of the combined b₁*, b₂* and b₃* values is less than        about 30% of the overall scale of possible b* values.    -   Clause 25. The article of any of the proceeding clauses, wherein        the range of the combined b₁*, b₂* and b₃* values is less than        about 20% of the overall scale of possible b* values.    -   Clause 26. The article of any of the proceeding clauses, wherein        the range of the combined b₁*, b₂* and b₃* values is less than        about 10% of the overall scale of possible b* values.    -   Clause 27. The article of any of the proceeding clauses, wherein        the optical element, as disposed onto the article, when measured        according to the CIE 1976 color space under a given illumination        condition at two observation angles between −15 degrees and +60        degrees, has a first color measurement at a first angle of        observation having coordinates L₁* and a₁* and b₁*, and a second        color measurement at a second angle of observation having        coordinates L₂* and a₂* and b_(2*), wherein the L₁* and L₂*        values may be the same or different, wherein the a₁* and a₂*        coordinate values may be the same or different, wherein the b₁*        and b₂* coordinate values may be the same or different, and        wherein the ΔE*_(ab) between the first color measurement and the        second color measurement is less than or equal to about 100,        where ΔE*_(ab)=[(L₁*-L₂*)²+(a₁*-a₂*)²+(b₁*-b₂*)²]^(1/2).    -   Clause 28. The article of any of the proceeding clauses, wherein        the ΔE*_(ab) between the first color measurement and the second        color measurement is less than or equal to about 80.    -   Clause 29. The article of any of the proceeding clauses, wherein        the ΔE*_(ab) between the first color measurement and the second        color measurement is less than or equal to about 60.    -   Clause 30. The article of any of the proceeding clauses, wherein        the optical element, as disposed onto the article, when measured        according to the CIELCH color space under a given illumination        condition at three observation angles between −15 degrees and        +60 degrees, has a first color measurement at a first angle of        observation having coordinates L₁* and C₁* and h₁°, and a second        color measurement at a second angle of observation having        coordinates L₂* and C₂* and h₂°, and a third color measurement        at a third angle of observation having coordinates L₃* and C₃*        and h₃°, wherein the L₁*, L₂*, and L₃* values may be the same or        different, wherein the C₁*, C₂*, and C₃* coordinate values may        be the same or different, wherein the h₁°, h₂° and h₃°        coordinate values may be the same or different, and wherein the        range of the combined h₁°, h₂° and h₃° values is less than about        60 degrees.    -   Clause 31. The article of any of the proceeding clauses, wherein        the range of the combined h₁°, h₂° and h₃° values is less than        about 50 degrees.    -   Clause 32. The article of any of the proceeding clauses, wherein        the range of the combined h₁°, h₂° and h₃° values is less than        about 40 degrees.    -   Clause 33. The article of any of the proceeding clauses, wherein        the range of the combined h₁°, h₂° and h₃° values is less than        about 30 degrees.    -   Clause 33. The article of any of the proceeding clauses, wherein        the range of the combined h₁°, h₂° and h₃° values is less than        about 35 degrees.    -   Clause 35. The article of any of the proceeding clauses, wherein        the range of the combined h₁°, h₂° and h₃° values is less than        about 20 degrees.    -   Clause 36. The article of any of the proceeding clauses, wherein        a primer layer is disposed on the textured surface.    -   Clause 37. The article of any of the proceeding clauses, wherein        the optical element is disposed on the structure adjacent the        primer layer.    -   Clause 38. The article of any of the proceeding clauses, wherein        the optical element is disposed on the first polymeric material        of the side of the article, with the primer layer, the textured        surface, or both, positioned between the optical element and the        first polymeric material.    -   Clause 39. The article of any of the proceeding clauses, wherein        the primer layer comprises a textured surface, and the textured        surface of the primer layer, the primer layer, and the optical        layer imparts the structural color.    -   Clause 40. The article of any of the proceeding clauses, wherein        the primer layer is formed from digital printing, offset        printing, pad printing, screen printing, flexographic printing,        or heat transfer printing.    -   Clause 41. The article of any of the proceeding clauses, wherein        the primer layer comprises a paint.    -   Clause 42. The article of any of the proceeding clauses, wherein        the primer layer comprises an ink.    -   Clause 43. The article of any of the proceeding clauses, wherein        the primer layer comprises a reground, and at least partially        degraded polymer.    -   Clause 44. The article of any of the proceeding clauses, wherein        the primer layer is an oxide layer.    -   Clause 45. The article of any of the proceeding clauses, wherein        the oxide layer is a metal oxide or a metal oxynitride.    -   Clause 46. The article of any of the proceeding clauses, wherein        the metal oxide or metal oxynitride is doped.    -   Clause 47. The article of any of the proceeding clauses, wherein        the primer layer is a coating, wherein the coating is a        crosslinked coating including a matrix of crosslinked polymers.    -   Clause 48. The article of any of the proceeding clauses, wherein        the coating comprises a plurality of solid pigment particles        entrapped in the matrix of crosslinked polymers.    -   Clause 49. The article of any of the proceeding clauses, wherein        the matrix of crosslinked polymers includes crosslinked        elastomeric polymers.    -   Clause 50. The article of any of the proceeding clauses, wherein        the crosslinked elastomeric polymers include crosslinked        polyurethane homopolymers or copolymers or both.    -   Clause 51. The article of any of the proceeding clauses, wherein        the crosslinked polyurethane copolymers include crosslinked        polyester polyurethanes.    -   Clause 52. The article of any of the proceeding clauses,        wherein, when the solid pigment particles are present, the solid        pigment particles are selected from the group consisting of:        metal and metal oxide pigments, carbon pigments, clay earth        pigments, ultramarine pigments and a combination thereof.    -   Clause 53. The article of any of the proceeding clauses, wherein        the coating further comprises a dye.    -   Clause 54. The article of any of the proceeding clauses,        wherein, when the dye is present, the dye is an acid dye.    -   Clause 55. The article of any of the proceeding clauses, wherein        the coating further comprises a quaternary ammonium compound.    -   Clause 56. The article of any of the proceeding clauses, wherein        the quaternary ammonium compound is a tetrabutyl ammonium        compound.    -   Clause 57. The article of any of the proceeding clauses, wherein        the tetrabutyl ammonium compound is a tetrabutyl ammonium        halide.    -   Clause 58. The article of any of the proceeding clauses, wherein        the polymeric coating composition, when present, comprises from        1 to 15 weight percent of the quaternary ammonium compound.    -   Clause 59. The article of any of the proceeding clauses, wherein        a molar ratio of the acid dye to the quaternary ammonium        compound ranges from 3:1 to 1:3    -   Clause 60. The article of any of the proceeding clauses, wherein        the molar ratio of the acid dye to the quaternary ammonium        compound ranges from 1.5:1 to 1:1.5.    -   Clause 61. The article of any of the proceeding clauses, wherein        the matrix of crosslinked polymers of the coating include        polyurethane polymers.    -   Clause 62. The article of any of the proceeding clauses, wherein        the polyurethane polymers include thermoplastic polyurethane        polymers.    -   Clause 63. The article of any of the proceeding clauses, wherein        the polyurethane polymers include elastomeric polyurethane        polymers.    -   Clause 64. The article of any of the proceeding clauses, wherein        the polyurethane polymers include polyester polyurethane        copolymers.    -   Clause 65. The article of any of the proceeding clauses, wherein        the polyurethane polymers consist essentially of polyester        polyurethane copolymers.    -   Clause 66. The article of any of the proceeding clauses, wherein        the primer layer has a thickness of about 3 to 200 nanometers.    -   Clause 67. The article of any of the proceeding clauses, wherein        the primer layer has a color selected from the group consisting        of: black, dark brown, dark red, dark orange, dark yellow, dark        green, dark cyan, dark blue, dark violet, grey, dark magenta,        dark indigo, tones thereof, tints thereof, shades thereof, and a        combination thereof.    -   Clause 68. The article of any of the proceeding clauses, wherein        the color of the primer layer is different than the color of the        structural color under the criteria in clauses 19 to 22.    -   Clause 69. The article of any of the proceeding clauses, wherein        the first polymeric material is a thermoplastic material.    -   Clause 70. The article of any of the proceeding clauses, wherein        the thermoplastic material comprises an elastomeric        thermoplastic material.    -   Clause 71. The article of any of the proceeding clauses, wherein        the thermoplastic material includes one or more thermoplastic        polyurethanes.    -   Clause 72. The article of any of the proceeding clauses, wherein        the elastomeric thermoplastic material includes one or more        thermoplastic polyurethanes, polyesters, polyamides,        polyolefins, or a combination thereof.    -   Clause 73. The article of any of the proceeding clauses, wherein        the elastomeric thermoplastic material includes one or more        thermoplastic polyurethanes.    -   Clause 74. The article of any of the proceeding clauses, wherein        the elastomeric thermoplastic material includes a polyester        polyurethane copolymer.    -   Clause 75. The article of any of the proceeding clauses, wherein        the first polymeric material is a thermoset material.    -   Clause 76. The article of any of the proceeding clauses, wherein        the structure includes a textile, and at least an outer layer of        the textile includes the first polymeric material.    -   Clause 77. The article of any of the proceeding clauses, wherein        the textile is a nonwoven textile.    -   Clause 78. The article of any of the proceeding clauses, wherein        the textile is a non-woven synthetic leather.    -   Clause 79. The article of any of the proceeding clauses, wherein        the textile is a woven textile.    -   Clause 80. The article of any of the proceeding clauses, wherein        the textile is knit textile.    -   Clause 81. The article of any of the proceeding clauses, wherein        the textile comprises a first fiber or a first yarn.    -   Clause 82. The article of any of the proceeding clauses, wherein        the first fiber or the first yarn includes at least an outer        layer formed of the first thermoplastic material.    -   Clause 83. The article of any of the proceeding clauses, wherein        a region of the first or second side of the structure onto which        the optical element is disposed includes the first fiber or the        first yarn in a non-filamentous conformation.    -   Clause 84. The article of any of the proceeding clauses, wherein        the structure includes a film, and at least an outer layer of        the film includes the first polymeric material.    -   Clause 85. The article of any of the proceeding clauses, wherein        the film is a multi-layer film.    -   Clause 86. The article of any of the proceeding clauses, wherein        the film has a gas transmission rate of 15 cm³/m²·atm·day or        less for nitrogen for an average film thickness of 20 mils.    -   Clause 87. The article of any of the proceeding clauses, wherein        the structure includes a foam, and at least an outer layer of        the foam includes the first polymeric material.    -   Clause 88. The article of any of the proceeding clauses, wherein        the structure includes a component formed of solid resin, and at        least an outer layer of the component includes the first        polymeric material.    -   Clause 89. The article of any of the proceeding clauses, wherein        the component formed of solid resin is a molded component.    -   Clause 90. The article of any of the proceeding clauses, wherein        the structure includes an additive manufactured component, and        at least an outer layer of the component includes the first        polymeric material.    -   Clause 91. The article of any of the proceeding clauses, wherein        the structure includes a bladder, and at least an outer layer of        the bladder includes the first polymeric material.    -   Clause 92. The article of any of the proceeding clauses, wherein        the bladder includes the textured surface, and the textured        surface is disposed on an externally-facing side or an        internally facing side of the bladder.    -   Clause 93. The article of any of the proceeding clauses, wherein        the second side of the optical element is disposed on an        internally facing side of the bladder.    -   Clause 94. The article of any of the proceeding clauses, wherein        the textured surface is disposed on the externally facing side        of the bladder.    -   Clause 95. The article of any of the proceeding clauses, wherein        the primer layer is disposed the second side of the optical        element, wherein the first side of the optical element is        disposed on the internally-facing side of the bladder.    -   Clause 96. The article of any of the proceeding clauses, wherein        the primer layer is disposed on an externally-facing side of the        bladder, wherein the optical element is disposed on the        externally-facing side of the bladder, with the primer layer,        the textured surface, or both, positioned between the optical        element and the externally-facing side of the bladder.    -   Clause 97. The article of any of the proceeding clauses, wherein        the structure is an upper.    -   Clause 98. The article of any of the proceeding clauses, wherein        the structure is a sole.    -   Clause 99. The article of any of the proceeding clauses, wherein        the structure is a cushioning element of a sole.    -   Clause 100. The article of any of the proceeding clauses,        wherein the structure is a bladder of a sole.    -   Clause 101. The article of any preceding clause, wherein the        structural color is visible to a viewer having 20/20 visual        acuity and normal color vision from a distance of about 1 meter        from the bladder.    -   Clause 102. The article of any preceding clause, wherein the        structural color has a single hue.    -   Clause 103. The article of any preceding clause, wherein the        structural color includes two or more hues.    -   Clause 104. The article of any preceding clause, wherein the        structural color is iridescent.    -   Clause 105. The article of any preceding clause, wherein the        structural color has limited iridescence.    -   Clause 106. The article of the preceding clause, wherein the        structural color has limited iridescence such that, when each        color visible at each possible angle of observation is assigned        to a single hue selected from the group consisting of the        primary, secondary and tertiary colors on the red yellow blue        (RYB) color wheel, all of the assigned hues fall into a single        hue group, wherein the single hue group is one of a)        green-yellow, yellow, and yellow-orange; b) yellow,        yellow-orange and orange; c) yellow-orange, orange, and        orange-red; d) orange-red, and red-purple; e) red, red-purple,        and purple; f) red-purple, purple, and purple-blue; g) purple,        purple-blue, and blue; h) purple-blue, blue, and blue-green; i)        blue, blue-green and green; and j) blue-green, green, and        green-yellow.    -   Clause 107. The article of the preceding clause wherein the        structural color having limited iridescence is limited to two or        three of the hues green-yellow, yellow, yellow-orange; or the        hues purple-blue, blue, and blue-green; or the hues orange-red,        red, and red-purple; or the hues blue-green, green, and        green-yellow; or the hues yellow-orange, orange, and orange-red;        or the hues red-purple, purple, and purple-blue.    -   Clause 108. The article of any preceding clause, wherein the        primer layer consists essentially of a metal oxide, optionally        titanium dioxide or silicon dioxide, and optionally consists        essentially of titanium dioxide.    -   Clause 109. The article of any preceding clause, wherein the        primer layer consists essentially of a doped metal oxide or a        doped metal oxynitride or both.    -   Clause 110. The article of any preceding clause, wherein the        primer layer has a thickness of about 1 to about 200        micrometers, or optionally of about 10 to about 100 micrometers,        or optionally of about 10 to about 80 micrometers.

Clause Set B

-   -   Clause 1. An article of footwear comprising:        -   a structure forming at least a portion of an upper or sole            of the article of footwear, the structure having a first            side; and        -   an optical element having a first side and a second side            opposing the first side, wherein the first side of the            optical element, the second side of the optical element, or            both impart a structural color,        -   wherein the first side of the optical element or the second            side of the optical element is disposed on the first side of            the structure.    -   Clause 2. The article of any of the proceeding clauses in clause        set A or B, wherein at least a portion of the first side of the        structure onto which the first side of the optical element or        the second side of the optical element is disposed includes a        first polymeric material, wherein the optical element is        disposed on the first polymeric material, with optionally a        primer layer, optionally a textured surface, or optionally both,        positioned between the optical element and the first polymeric        material.    -   Clause 3. The article of any of the proceeding clauses in clause        set A or B, wherein the textured surface includes a plurality of        profile features and flat planar areas, wherein the profile        features extend above the flat areas of the textured surface,        wherein the profile features and the flat areas result in at        least one layer of the optical element having an undulating        topography, wherein there is a planar region between neighboring        elevated or depressed regions that is planar with the flat        planar areas of the textured surface, wherein the dimensions of        the profile features, a shape of the profile features, a spacing        among the plurality of the profile features, in combination with        the optical element impart the structural color.    -   Clause 4. The article of any of the proceeding clauses in clause        set A or B, wherein the optical element includes at least one        optical layer, wherein at least one of the layers of the optical        element has a thickness that is about one fourth of the        wavelength of visible light to be reflected by the optical        element to produce the structural color.    -   Clause 5. The article of any of the proceeding clauses in clause        set A or B, wherein the optical element, as disposed on the        structure, when measured according to the CIE 1976 color space        under a given illumination condition at three observation angles        between −15 degrees and +60 degrees, has a first color        measurement at a first angle of observation having coordinates        L₁* and a₁* and b₁*, and a second color measurement at a second        angle of observation having coordinates L₂* and a₂* and b₂*, and        a third color measurement at a third angle of observation having        coordinates L₃* and a₃* and b_(3*), wherein the L₁*, L₂*, and        L₃* values may be the same or different, wherein the a₁*,        a_(2*), and a₃* coordinate values may be the same or different,        wherein the b₁*, b₂*, and b₃* coordinate values may be the same        or different, and wherein the range of the combined a₁*, a₂* and        a₃* values is less than about 40% of the overall scale of        possible a* values.    -   Clause 6. The article of any of the proceeding clauses in clause        set A or B, wherein the structure includes a textile selected        from a nonwoven textile, a woven textile, a knit textile, or a        synthetic leather, and at least an outer layer of the textile        includes the first polymeric material.    -   Clause 7. The article of any of the proceeding clauses in clause        set A or B, wherein the structure includes a film, and at least        an outer layer of the film includes the first polymeric        material, wherein the film has a gas transmission rate of 15        cm³/m²·atm·day or less for nitrogen for an average film        thickness of 20 mils, and wherein optionally the film is a        multi-layer film.    -   Clause 8. The article of any of the proceeding clauses in clause        set A or B, wherein the structure includes a bladder, and at        least an outer layer of the bladder includes the first polymeric        material, and optionally, wherein the bladder includes the        textured surface, and when present, the optional textured        surface is disposed on an externally-facing side or an        internally facing side of the bladder.    -   Clause 9. The article of any of the proceeding clauses in clause        set A or B, wherein the first side of the optical element is        disposed on an internally-facing side of the bladder, optionally        with a primer layer, a textured surface, or both, positioned on        the second side of the optical element; or the optical element        is disposed on an externally-facing side of the bladder,        optionally with the primer layer, optionally the optional        textured surface, or both, positioned between the optical        element and the externally-facing side of the bladder.    -   Clause 10. The article of any of the proceeding clauses in        clause set A or B, wherein the structure is an upper or a sole        or a combination of both an upper and a sole; when the structure        is optionally the sole, the structure is optionally a cushioning        element; and the optional cushioning element is optionally a        foam midsole or a bladder or both a foam midsole and a bladder.

Clause Set C

-   -   Clause 1. A method of making an article of footwear comprising:        -   providing an article of footwear comprising: a structure            forming at least a portion of an upper or sole of the            article of footwear, the structure having a first side; and            an optical element having a first side and a second side            opposing the first side, wherein the first side of the            optical element, the second side of the optical element, or            both impart a structural color; and        -   disposing the first side of the optical element or the            second side of the optical element onto the first side of            the structure.    -   Clause 2. The method of any one of the proceeding clauses,        wherein at least a portion of the first side of the structure,        onto which the first side of the optical element is disposed or        onto which the second side of the optical element is disposed,        includes a first polymeric material.    -   Clause 3. The method of any one of the proceeding clauses,        wherein the first side of the structure is an externally-facing        side.    -   Clause 4. The method of any one of the proceeding clauses,        wherein the at least a portion of the first side of the        structure or the optical element or both further comprise a        textured surface, and a combination of the textured surface and        the optical element imparts the structural color.    -   Clause 5. The method of any one of the proceeding clauses,        wherein the textured surface is part of a textured surface.    -   Clause 6. The method of any one of the proceeding clauses,        wherein the optical element comprises the textured surface.    -   Clause 7. The method of any one of the proceeding clauses,        wherein the textured surface is on the first side of the optical        element.    -   Clause 8. The method of any one of the proceeding clauses,        wherein the textured surface has a plurality of profile features        and plurality of flat areas.    -   Clause 9. The method of any one of the proceeding clauses,        wherein the textured surface includes a plurality of profile        features and flat planar areas, wherein the profile features        extend above the flat areas of the textured surface.    -   Clause 10. The method of any one of the proceeding clauses,        wherein the dimensions of the profile features, a shape of the        profile features, and a spacing among the plurality of the        profile features, in combination with the optical element,        create the structural color.    -   Clause 11. The method of any one of the proceeding clauses,        wherein, over an area of the textured surface having a surface        area of at least 5 square millimeters, the profile features are        in random positions relative to one another.    -   Clause 12. The method of any one of the proceeding clauses,        wherein the spacing among the profile features reduces        distortion effects of the profile features from interfering with        one another in regard to the structural color.    -   Clause 13. The method of any one of the proceeding clauses,        wherein the profile features and the flat areas result in at        least one layer of the optical layer having an undulating        topography across the textured surface, wherein there is a        planar region between neighboring profile features that is        planar with the flat planar areas of the textured surface,        wherein the planar region has dimensions relative to the profile        features to impart the structural color.    -   Clause 14. The method of any one of the proceeding clauses,        herein the profile features and the flat areas result in each        layer of the optical layer having an undulating topography        across the textured surface.    -   Clause 15. The method of any one of the proceeding clauses,        wherein the optical element includes an optical layer, wherein        the optical layer comprises a multilayer reflector or a        multilayer filter.    -   Clause 16. The method of any one of the proceeding clauses,        wherein the multilayer reflector has at least two layers,        including at least two adjacent layers having different        refractive indices.    -   Clause 17. The method of any one of the proceeding clauses,        wherein at least one of the layers of the multilayer reflector        has a thickness that is about one fourth of the wavelength of        visible light to be reflected by the optical element to produce        the structural color.    -   Clause 18. The method of any one of the proceeding clauses,        wherein at least one of the layers of the multilayer reflector        comprises a material selected from the group consisting of:        silicon dioxide, titanium dioxide, zinc sulfide, magnesium        fluoride, tantalum pentoxide, and a combination thereof.    -   Clause 19. The method of any one of the proceeding clauses,        wherein the optical element, as disposed onto the article, when        measured according to the CIE 1976 color space under a given        illumination condition at three observation angles between −15        degrees and +60 degrees, has a first color measurement at a        first angle of observation having coordinates L₁* and a₁* and        b₁*, and a second color measurement at a second angle of        observation having coordinates L₂* and a₂* and b₂*, and a third        color measurement at a third angle of observation having        coordinates L₃* and a₃* and b_(3*), wherein the L₁*, L_(2*), and        L₃* values may be the same or different, wherein the a₁*,        a_(2*), and a₃* coordinate values may be the same or different,        wherein the b₁*, b₂*, and b₃* coordinate values may be the same        or different, and wherein the range of the combined a₁*, a₂* and        a₃* values is less than about 40% of the overall scale of        possible a* values.    -   Clause 20. The method of any one of the proceeding clauses,        wherein the range of the combined a₁*, a₂* and a₃* values is        less than about 30% of the overall scale of possible a* values.    -   Clause 21. The method of any one of the proceeding clauses,        wherein the range of the combined a₁*, a₂* and a₃* values is        less than about 20% of the overall scale of possible a* values.    -   Clause 22. The method of any one of the proceeding clauses,        wherein the range of the combined a₁*, a₂* and a₃* values is        less than about 25% of the overall scale of possible a* values.    -   Clause 23. The method of any one of the proceeding clauses,        wherein the range of the combined a₁*, a₂* and a₃* values is        less than about 10% of the overall scale of possible a* values.    -   Clause 24. The method of any one of the proceeding clauses,        wherein the optical element, as disposed onto the article, when        measured according to the CIE 1976 color space under a given        illumination condition at three observation angles between −15        degrees and +60 degrees, has a first color measurement at a        first angle of observation having coordinates L₁* and a₁* and        b₁*, and a second color measurement at a second angle of        observation having coordinates L₂* and a₂* and b₂*, and a third        color measurement at a third angle of observation having        coordinates L₃* and a₃* and b_(3*), wherein the L₁*, L_(2*), and        L₃* values may be the same or different, wherein the a₁*,        a_(2*), and a₃* coordinate values may be the same or different,        wherein the b₁*, b₂*, and b₃* coordinate values may be the same        or different, and wherein the range of the combined b₁*, b₂* and        b₃* values is less than about 40% of the overall scale of        possible b* values.    -   Clause 25. The method of any one of the proceeding clauses,        wherein the range of the combined b₁*, b₂* and b₃* values is        less than about 30% of the overall scale of possible b* values.    -   Clause 26. The method of any one of the proceeding clauses,        wherein the range of the combined b₁*, b₂* and b₃* values is        less than about 20% of the overall scale of possible b* values.    -   Clause 27. The method of any one of the proceeding clauses,        wherein the range of the combined b₁*, b₂* and b₃* values is        less than about 10% of the overall scale of possible b* values.    -   Clause 28. The method of any one of the proceeding clauses,        wherein the optical element, as disposed onto to the article,        when measured according to the CIE 1976 color space under a        given illumination condition at two observation angles between        −15 degrees and +60 degrees, has a first color measurement at a        first angle of observation having coordinates L₁* and a₁* and        b₁*, and a second color measurement at a second angle of        observation having coordinates L₂* and a₂* and b_(2*), wherein        the L₁* and L₂* values may be the same or different, wherein the        a₁* and a₂* coordinate values may be the same or different,        wherein the b₁* and b₂* coordinate values may be the same or        different, and wherein the ΔE*_(ab) between the first color        measurement and the second color measurement is less than or        equal to about 100, where        ΔE*_(ab)=[(L₁*-L₂*)²+(a₁*-a₂*)²+(b₁*-b₂*)²]^(1/2).    -   Clause 29. The method of any one of the proceeding clauses,        wherein the ΔE*_(ab) between the first color measurement and the        second color measurement is less than or equal to about 80.    -   Clause 30. The method of any one of the proceeding clauses,        wherein the ΔE*_(ab) between the first color measurement and the        second color measurement is less than or equal to about 60.    -   Clause 31. The method of any one of the proceeding clauses,        wherein the optical element, as disposed onto to the article,        when measured according to the CIELCH color space under a given        illumination condition at three observation angles between −15        degrees and +60 degrees, has a first color measurement at a        first angle of observation having coordinates L₁* and C₁* and        h₁°, and a second color measurement at a second angle of        observation having coordinates L₂* and C₂* and h₂°, and a third        color measurement at a third angle of observation having        coordinates L₃* and C₃* and h₃°, wherein the L₁*, L_(2*), and        L₃* values may be the same or different, wherein the C₁*, C₂*,        and C₃* coordinate values may be the same or different, wherein        the h₁°, h₂° and h₃° coordinate values may be the same or        different, and wherein the range of the combined h₁°, h₂° and        h₃° values is less than about 60 degrees.    -   Clause 32. The method of any one of the proceeding clauses,        wherein the range of the combined h₁°, h₂° and h₃° values is        less than about 50 degrees.    -   Clause 33. The method of any one of the proceeding clauses,        wherein the range of the combined h₁°, h₂° and h₃° values is        less than about 40 degrees.    -   Clause 34. The method of any one of the proceeding clauses,        wherein the range of the combined h₁°, h₂° and h₃° values is        less than about 30 degrees.    -   Clause 35. The method of any one of the proceeding clauses,        wherein the range of the combined h₁°, h₂° and h₃° values is        less than about 20 degrees.    -   Clause 36. The method of any one of the proceeding clauses,        wherein a primer layer is disposed between the optical element        and the structure.    -   Clause 37. The method of any one of the proceeding clauses,        wherein the textured surface is present, and the primer layer is        disposed between the textured surface and the optical element    -   Clause 38. The method of any one of the proceeding clauses,        wherein the optical element is disposed on the first polymeric        material of the first side of the structure, with the primer        layer, the textured surface, or both, positioned between the        optical element and the first polymeric material.    -   Clause 39. The method of any one of the proceeding clauses,        wherein the primer layer comprises a textured surface, and a        combination of the textured surface of the primer layer, the        primer layer, and the optical element impart the structural        color.    -   Clause 40. The method of any one of the proceeding clauses,        wherein the primer layer is a digitally printed primer layer, an        offset printed primer layer, a pad printed primer layer, a        screen printed primer layer, a flexographically printed primer        layer, or a heat transfer printed primer layer.    -   Clause 41. The method of any one of the proceeding clauses,        wherein the primer layer comprises a paint.    -   Clause 42. The method of any one of the proceeding clauses,        wherein the primer layer comprises an ink.    -   Clause 43. The method of any one of the proceeding clauses,        wherein the primer layer comprises a reground, and at least        partially degraded, polymer.    -   Clause 44. The method of any one of the proceeding clauses,        wherein the primer layer is an oxide layer.    -   Clause 45. The method of any one of the proceeding clauses,        wherein the oxide layer is a metal oxide or a metal oxynitride.    -   Clause 46. The method of any one of the proceeding clauses,        wherein the metal oxide or metal oxynitride is doped.    -   Clause 47. The method of any one of the proceeding clauses,        wherein the primer layer is a coating, and wherein the coating        is a crosslinked coating including a matrix of crosslinked        polymers.    -   Clause 48. The method of any one of the proceeding clauses,        wherein the coating comprises a plurality of solid pigment        particles entrapped in the matrix of crosslinked polymers.    -   Clause 49. The method of any one of the proceeding clauses,        wherein the matrix of crosslinked polymers includes crosslinked        elastomeric polymers.    -   Clause 50. The method of any one of the proceeding clauses,        wherein the crosslinked elastomeric polymers include crosslinked        polyurethane homopolymers or copolymers or both.    -   Clause 51. The method of any one of the proceeding clauses,        wherein the crosslinked polyurethane copolymers include        crosslinked polyester polyurethanes.    -   Clause 52. The method of any one of the proceeding clauses,        wherein the primer layer is a coating, the coating is a product        of crosslinking a polymeric coating composition, and the        polymeric coating composition comprises a dispersion of        polymers.    -   Clause 53. The method of any one of the proceeding clauses,        wherein the dispersion of polymers is a water-borne dispersion        of polymers.    -   Clause 54. The method of any one of the proceeding clauses,        wherein the polymeric coating composition further comprises a        crosslinking agent.    -   Clause 55. The method of any one of the proceeding clauses,        wherein the crosslinking agent is a water-borne crosslinking        agent.    -   Clause 56. The method of any one of the proceeding clauses,        wherein the polymeric coating composition further comprises a        plurality of solid pigment particles mixed with the dispersion        of polymers.    -   Clause 57. The method of any one of the proceeding clauses,        wherein the polymeric coating composition further comprises a        solubilized dye.    -   Clause 58. The method of any one of the proceeding clauses,        wherein the polymeric coating composition further comprises an        organic solvent.    -   Clause 59. The method of any one of the proceeding clauses,        wherein the organic solvent is a water-miscible organic solvent.    -   Clause 60. The method of any one of the proceeding clauses,        wherein, when the solid pigment particles are present, the solid        pigment particles are selected from the group consisting of:        metal and metal oxide pigments, carbon pigments, clay earth        pigments, ultramarine pigments and a combination thereof.    -   Clause 61. The method of any one of the proceeding clauses,        wherein the coating further comprises a dye.    -   Clause 62. The method of any one of the proceeding clauses,        wherein, when the dye is present, the dye is an acid dye.    -   Clause 63. The method of any one of the proceeding clauses,        wherein the coating further comprises a quaternary ammonium        compound.    -   Clause 64. The method of any one of the proceeding clauses,        wherein the quaternary ammonium compound is a tetrabutyl        ammonium compound.    -   Clause 65. The method of any one of the proceeding clauses,        wherein the tetrabutyl ammonium compound is a tetrabutyl        ammonium halide.    -   Clause 66. The method of any one of the proceeding clauses,        wherein the polymeric coating composition, when present,        comprises from 1 to 15 weight percent of the quaternary ammonium        compound    -   Clause 67. The method of any one of the proceeding clauses,        wherein a molar ratio of the acid dye to the quaternary ammonium        compound ranges from 3:1 to 1:3    -   Clause 68. The method of any one of the proceeding clauses,        wherein the molar ratio of the acid dye to the quaternary        ammonium compound ranges from 1.5:1 to 1:1.5.    -   Clause 69. The method of any one of the proceeding clauses,        wherein the matrix of crosslinked polymers of the coating or the        polymeric coating composition include polyurethane polymers.    -   Clause 70. The method of any one of the proceeding clauses,        wherein the polyurethane polymers include thermoplastic        polyurethane polymers.    -   Clause 71. The method of any one of the proceeding clauses,        wherein the polyurethane polymers include elastomeric        polyurethane polymers.    -   Clause 72. The method of any one of the proceeding clauses,        wherein the polyurethane polymers include polyester polyurethane        copolymers.    -   Clause 73. The method of any one of the proceeding clauses,        wherein the polyurethane polymers consist essentially of        polyester polyurethane copolymers.    -   Clause 74. The method of any one of the proceeding clauses,        wherein the primer layer has a thickness of about 3 to 200        nanometers.    -   Clause 75. The method of any one of the proceeding clauses,        wherein the primer layer has a color selected from the group        consisting of: black, dark brown, dark red, dark orange, dark        yellow, dark green, dark cyan, dark f blue, dark violet, grey,        dark magenta, dark indigo, tones thereof, tints thereof, shades        thereof, and a combination thereof.    -   Clause 76. The method of any one of the proceeding clauses,        wherein the color of the primer layer is different than the        color of the structural color.    -   Clause 77. The method of any one of the proceeding clauses,        wherein the color of the primer layer is different than the        color of the structural color under the criteria in clauses 19        to 22.    -   Clause 78. The method of any one of the proceeding clauses,        wherein the first polymeric material is a thermoplastic material        comprising at least one thermoplastic polymer.    -   Clause 79. The method of any one of the proceeding clauses,        wherein the thermoplastic material is an elastomeric        thermoplastic material.    -   Clause 80. The method of any one of the proceeding clauses,        wherein the thermoplastic material includes one or more        thermoplastic polyurethanes.    -   Clause 81. The method of any one of the proceeding clauses,        wherein the thermoplastic material includes one or more        thermoplastic polyurethanes, polyesters, polyamides,        polyolefins, or a combination thereof.    -   Clause 82. The method of any one of the proceeding clauses,        wherein the thermoplastic material includes a polyester        polyurethane copolymer.    -   Clause 83. The method of any one of the proceeding clauses,        wherein the first polymeric material is a thermoset material        comprising at least one thermoset polymer.    -   Clause 84. The method of any one of the proceeding clauses,        wherein the first side of the structure includes a textile, and        at least an outer layer of the textile includes the first        polymeric material.    -   Clause 85. The method of any one of the proceeding clauses,        wherein the textile is a nonwoven textile.    -   Clause 86. The method of any one of the proceeding clauses,        wherein the nonwoven textile is a non-woven synthetic leather.    -   Clause 87. The method of any one of the proceeding clauses,        wherein the textile is a woven textile.    -   Clause 88. The method of any one of the proceeding clauses,        wherein the textile is a knit textile.    -   Clause 89. The method of any one of the proceeding clauses,        wherein the textile comprises a first fiber or a first yarn.    -   Clause 90. The method of any one of the proceeding clauses,        wherein the first fiber or the first yarn includes at least an        outer layer formed of the first thermoplastic material.    -   Clause 91. The method of any one of the proceeding clauses,        wherein a region of the first side of the structure onto which        the optical element is disposed on includes the first fiber or        the first yarn in a non-filamentous conformation.    -   Clause 92. The method of any one of the proceeding clauses,        wherein the first side of the structure includes a film, and at        least an outer layer of the film includes the first polymeric        material.    -   Clause 93. The method of any one of the proceeding clauses,        wherein the film is a multi-layer film.    -   Clause 94. The method of any one of the proceeding clauses,        wherein the film has a gas transmission rate of 15        cm³/m²·atm·day or less for nitrogen for an average film        thickness of 20 mils.    -   Clause 95. The method of any one of the proceeding clauses,        wherein the first side of the structure includes a foam, and at        least an outer layer of the foam includes the first polymeric        material.    -   Clause 96. The method of any one of the proceeding clauses,        wherein the first side of the structure includes a component        formed of solid resin, and at least an outer layer of the        component includes the first polymeric material.    -   Clause 97. The method of any one of the proceeding clauses,        wherein the component formed of solid resin is a molded        component.    -   Clause 98. The method of any one of the proceeding clauses,        wherein the first side of the structure includes an additive        manufactured component, and at least an outer layer of the        component includes the first polymeric material.    -   Clause 99. The method of any one of the proceeding clauses,        wherein the first side of the structure includes an        externally-facing side of a bladder or an internally-facing side        of a bladder, and at least an outer layer of the bladder on the        externally-facing side or on the internally-facing side includes        the first polymeric material.    -   Clause 100. The method of any one of the proceeding clauses,        wherein the bladder includes the textured surface on the        externally-facing side or on the internally-facing side, and the        first side of the optical element or the second side of the        optical element is disposed on the textured surface.    -   Clause 101. The method of any one of the proceeding clauses,        wherein the second side of the optical element is disposed on        the internally-facing side of the bladder.    -   Clause 102. The method of any one of the proceeding clauses,        wherein the textured surface is disposed on the        externally-facing side of the bladder.    -   Clause 103. The method of any one of the proceeding clauses,        wherein the first side of the optical element is disposed on the        internally-facing side of the bladder, with the primer layer,        the textured surface, or both, positioned on the second side of        the optical element.    -   Clause 104. The method of any one of the proceeding clauses,        wherein the first side of the optical element is disposed on the        externally-facing side of the bladder, with the primer layer,        the textured surface, or both, positioned between the first side        of the optical element and the externally-facing side of the        bladder.    -   Clause 105. The method of any one of the proceeding clauses,        wherein the structure is an upper.    -   Clause 106. The method of any one of the proceeding clauses,        wherein the structure is a sole.    -   Clause 107. The method of any one of the proceeding clauses,        wherein the structure is a cushioning element of a sole.    -   Clause 108. The method of any one of the proceeding clauses,        wherein the structure is a bladder of a sole.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 weight percent toabout 5 weight percent but also include individual concentrations (e.g.,1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4percent) within the indicated range. The term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

Many variations and modifications may be made to the above-describedembodiments. All such modifications and variations are intended to beincluded herein within the scope of this disclosure and protected by thefollowing claims.

What is claimed is:
 1. An article comprising: a component forming atleast a portion of the article, the component having a first surface;and an optical element having a first side and a second side opposingthe first side, wherein the first side of the optical element, thesecond side of the optical element, or both impart a structural color tothe component; wherein the first side of the optical element or thesecond side of the optical element is disposed on the first surface ofthe component, wherein the first surface includes a first area and asecond area, wherein the first area includes a primer layer, a texturedsurface, or both, that are disposed between the optical element and thefirst polymeric material, wherein the second area does not include theprimer layer, the textured layer, or both, wherein the optical elementon the first area imparts a first structural color, wherein the opticalelement on the second area imparts a second structural color, whereinthe first structural color and the second structural color aredifferent.
 2. The article of claim 1, wherein in the second area theoptical element is disposed directly onto the first polymeric material.3. The article of claim 1, wherein the textured surface includes aplurality of profile features and flat planar areas, wherein the profilefeatures extend above the flat areas of the textured surface, whereinthe profile features and the flat areas result in at least one layer ofthe optical element having an undulating topography, wherein there is aplanar region between neighboring elevated or depressed regions that isplanar with the flat planar areas of the textured surface, whereindimensions of the profile features, a shape of the profile features, aspacing among the plurality of the profile features, in combination withthe optical element impart the first structural color.
 4. The article ofclaim 1, wherein the optical element includes (i) multiple layers whereeach layer independently comprises a material selected from nitrides,oxynitrides, sulphides, sulfates, selenides and tellurides of atransition metal, a metalloid, a lanthanide and an actinide, (ii) one ormore layers made of liquid crystals, or (iii) one or more layers made ofsilicon dioxide, titanium dioxide, zinc sulphide, magnesium fluoride,tantalum pentoxide, aluminium oxide or a combination thereof.
 5. Thearticle of claim 1, wherein the first surface of the component includesa textile, wherein at least an outer layer of the textile includes thefirst polymeric material.
 6. The article of claim 5, wherein the textileis a nonwoven textile, a woven textile, or a knit textile.
 7. Thearticle of claim 1, wherein the first surface of the component includesa film, and at least an outer layer of the film includes the firstpolymeric material.
 8. The article of claim 7, wherein the film has agas transmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage film thickness of 20 mils.
 9. The article of claim 7, whereinthe film is a multi-layer film.
 10. The article of claim 9, wherein thefirst surface of the component includes a surface of a bladder, and atleast an outer layer of the bladder includes the first polymericmaterial.
 11. The article of claim 10, wherein the surface of thebladder includes the textured surface, and the surface of the bladder isan externally-facing surface of bladder or an internally facing surfaceof the bladder.
 12. The article of claim 11, wherein the first side ofthe optical element is disposed on the internally-facing surface of thebladder.
 13. The article of claim 1, wherein the article is an articleof footwear, and the component forms at least part of an upper or a soleor a combination of both an upper and a sole.
 14. The article of claim1, wherein the article is an article of apparel.
 15. The article ofclaim 1, wherein the article is a sporting good.
 16. The article ofclaim 1, wherein the first structural color is a multi-hued structuralcolor varies between two hues when viewed from two different viewingangles that are at least 15 degrees apart from each other.
 17. Thearticle of claim 1, wherein the first structural color is a multi-huedstructural color varies among three hues when viewed from differentviewing angles that are at least 15 degrees apart from each other. 18.The article of claim 1, wherein the first structural color is a themulti-hued structural color changes abruptly between 2-4 hues as anangle of observation or illumination changes by an observer having 20/20visual acuity and normal color vision from a distance of about 1 meterfrom the article.
 19. The article of claim 1, wherein the firststructural color is a multi-hued structural color and the secondstructural color is a single-hued structural color.
 20. The article ofclaim 1, wherein the first structural color is a single-hued structuralcolor and the second structural color is a single-hued structural color.